Electromagnetic state sensing devices

ABSTRACT

A container includes a surface defining a volume of the container, a first resonance portion disposed on a first portion of the surface of the container using one or more first carbon-based inks, and a second resonance portion disposed on a second portion of the surface of the container using one or more second carbon-based inks different than the one or more first carbon-based inks. The first resonance portion can resonate within a first range of frequencies in response to one or more electromagnetic pings received from a user device, and the second resonance portion can resonate within a second range of frequencies in response to the one or more electromagnetic pings, the second range of frequencies being different than the first range of frequencies. In some instances, the user device may be a smartphone, a radio frequency identification (RFID) reader, or a near-field communication (NFC) device.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is a continuation of U.S. patent applicationSer. No. 18/073,055 entitled “ELECTROMAGNETIC STATE SENSING DEVICES” andfiled on Dec. 1, 2022, which is a continuation of U.S. patentapplication Ser. No. 17/693,649 entitled “ELECTROMAGNETIC STATE SENSINGDEVICES” and filed on Mar. 14, 2022, now U.S. Pat. No. 11,537,806 B2,which is a continuation of U.S. patent application Ser. No. 17/153,146entitled “ELECTROMAGNETIC STATE SENSING DEVICES” and filed on Jan. 20,2021, now U.S. Pat. No. 11,288,466 B2, which is a continuation of U.S.patent application Ser. No. 16/530,173 entitled “ELECTROMAGNETIC STATESENSING DEVICES” and filed on Aug. 2, 2019, now U.S. Pat. No. 10,943,076B2, which claims priority to U.S. Provisional Patent Application No.62/716,741 entitled “PRODUCT SENSING” and filed on Aug. 9, 2018, all ofwhich are assigned to the assignee hereof. The disclosures of all priorapplications are considered part of and are incorporated by reference inthis patent application.

TECHNICAL FIELD

This disclosure relates generally to sensors, and more particularly, toradio-frequency (RF) sensing devices.

DESCRIPTION OF RELATED ART

Sensors are widely used for many purposes, and typically utilizeelectromagnetic signals to receive and send information. For example,radiofrequency identification (RFID) tags send information to an RFIDreader, where in the case of passive RFID tags, a tag utilizes energyfrom an interrogating signal to power the tag and send a signal back tothe reader. Conventional techniques for use of electromagnetic sensingdevices exhibit many deficiencies, therefore, what is needed is atechnique or techniques that address such deficiencies.

SUMMARY

This Summary is provided to introduce in a simplified form a selectionof subjects that are further described below in the DetailedDescription. This Summary is not intended to identify key features oressential features of the claimed subject matter, nor is it intended tolimit the scope of the claimed subject matter. Moreover, the systems,methods, and devices of this disclosure each have several innovativeaspects, no single one of which is solely responsible for the desirableattributes disclosed herein.

One innovative aspect of the subject matter described in this disclosurecan be implemented in a container. In some implementations, thecontainer may include a surface defining a volume of the container, afirst resonance portion disposed on a first portion of the surface ofthe container using one or more first carbon-based inks, and a secondresonance portion disposed on a second portion of the surface of thecontainer using one or more second carbon-based inks different than theone or more first carbon-based inks. The first resonance portion canresonate within a first range of frequencies in response to one or moreelectromagnetic pings received from a user device, and the secondresonance portion can resonate within a second range of frequencies inresponse to the one or more electromagnetic pings, the second range offrequencies being different than the first range of frequencies. In someinstances, the user device may be a smartphone, a radio frequencyidentification (RFID) reader, or a near-field communication (NFC)device.

The first resonance portion may include a first assembly ofthree-dimensional (3D) carbon-containing structures printed on the firstportion of the surface of the container, and the second resonanceportion may include a second assembly of 3D carbon-containing structuresprinted on the second portion of the surface of the container. In someinstances, a resonant frequency of the first resonance portion is basedat least in part on a geometry of the first portion of the surface ofthe container, and a resonant frequency of the second resonance portionis based at least in part on a geometry of the second portion of thesurface of the container. In some aspects, the first portion of thesurface of the container has a different physical geometry than thesecond portion of the surface of the container. In other aspects, aresonant frequency of at least one of the first resonance portion or thesecond resonance portion is based at least in part on the permeabilityof the container.

In some implementations, the first resonance portion can indicate apresence of an item within the container by resonating within the firstrange of frequencies in response to the one or more electromagneticpings. In some instances, the item includes an analyte, and the resonantfrequency of the first resonance portion is based at least in part onone or more characteristics of the analyte. In other instances, thesecond resonance portion can indicate state information of the item byresonating within the second range of frequencies in response to the oneor more electromagnetic pings. The state information may include one ormore of a quantity of the item within the container, a potency of theitem within the container, or a staleness of the item within thecontainer.

In other implementations, the container may also include a thirdresonance portion disposed on a third portion of the surface of thecontainer using one or more third carbon-based inks different than theone or more first carbon-based inks and the one or more secondcarbon-based inks. The third resonance portion can resonate within athird range of frequencies in response to the one or moreelectromagnetic pings. In some instances, the third resonance portioncan indicate product identification information of the item byresonating within the third range of frequencies in response to the oneor more electromagnetic pings. In some aspects, the productidentification information includes a product code or a product ID ofthe item. In other instances, the first resonance portion includes afirst assembly of 3D carbon-containing structures printed on the firstportion of the surface of the container, the second resonance portionincludes a second assembly of 3D carbon-containing structures printed onthe second portion of the surface of the container, and the thirdresonance portion includes a third assembly of 3D carbon-containingstructures printed on the third portion of the surface of the container,where each of the first, second, and third assemblies of 3Dcarbon-containing structures can resonate at a different frequency inresponse to the one or more electromagnetic pings.

In some other implementations, the first resonance portion can indicatea presence of an analyte by resonating at a first frequency in responseto the one or more electromagnetic pings, and indicate an absence of theanalyte by resonating at a second frequency in response to the one ormore electromagnetic pings, the second frequency being different thanthe first frequency. In some instances, the first resonance portionincludes a material that is sensitive to the presence of the analyte. Insome aspects, a capacitance of the material is based at least in part onthe presence of the analyte within the container. In other aspects, thematerial includes a redox mediator.

Details of one or more implementations of the subject matter describedin this disclosure are set forth in the accompanying drawings and thedescription below. Other features, aspects, and advantages will becomeapparent from the description, the drawings and the claims. Note thatthe relative dimensions of the following figures may not be drawn toscale.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts an environment in which electromagnetic state sensingdevices can be deployed, according to an embodiment.

FIG. 2 presents a flow chart depicting a processing flow by whichelectromagnetic state sensing devices can be deployed, according to anembodiment.

FIG. 3A is a schematic of an electromagnetic state sensing device,according to an embodiment.

FIG. 3B1 illustrates a deployment scenario in which a first state ofliquid contents is measured, according to an embodiment.

FIG. 3B2 illustrates a deployment scenario in which a second state ofliquid contents is measured, according to an embodiment.

FIG. 3B3 illustrates a deployment scenario in which a state of liquidcontents is measured and displayed, according to an embodiment.

FIG. 3B4 illustrates a cross-sectional view of a printed display forindicating the state of contents of a product, according to anembodiment.

FIG. 3C is a selection chart for determining a dynamic range of anelectromagnetic state sensing device, according to an embodiment.

FIG. 4A1 and FIG. 4A2 are equivalent circuit models of anelectromagnetic state sensing device in a first environment and a secondenvironment, respectively, according to an embodiment.

FIG. 4B depicts an empirical data capture technique as used forcalibrating electromagnetic state sensing devices in differentenvironments, according to an embodiment.

FIG. 5A depicts a signature capture technique as used forelectromagnetic state sensing, according to an embodiment.

FIG. 5B depicts a signature analysis technique as used forelectromagnetic state sensing, according to an embodiment.

FIG. 6 depicts a virtual assistant as used as a hub in a replenishmentsystem, according to an embodiment.

FIG. 7A presents a rule codification technique as used in areplenishment system based on electromagnetic state sensing devices,according to an embodiment.

FIG. 7B presents a rule execution technique as used in a replenishmentsystem based on electromagnetic state sensing devices, according to anembodiment.

FIG. 8 depicts an example protocol as used in a replenishment systembased on electromagnetic state sensing devices, according to anembodiment.

FIG. 9 depicts system components as arrangements of computing modulesthat are interconnected so as to implement certain of theherein-disclosed embodiments.

FIG. 10A through FIG. 10Y depict structured carbons, various carbonnanoparticles, various carbon-based aggregates, and variousthree-dimensional carbon-containing assemblies that are grown over othermaterials, according to some embodiments.

Like reference numbers and designations in the various drawings indicatelike elements.

DETAILED DESCRIPTION

Aspects of the present disclosure solve problems associated with how toinexpensively deploy state sensors. Some embodiments are directed toapproaches for printing sensing devices that can emit not onlyidentification information, but also product state information.

Various methods for identification of a product in its packaging havebeen in use since the dawn of eCommerce. However, mere identification ofthe existence of a product at a particular location and time fails toaddress a consumer's need for ongoing automatic status checks onproducts that are in or near the consumer's residence, car, boat, etc.Unfortunately, neither conventional radio frequency identifiers (RFIDs)nor conventional near-field labels are able to provide this information.As such, there is a need for new types of sensing devices that can emitnot only product identification information, but also product stateinformation in a manner that can be read by a mobile reader orstationary scanner.

Various methods for identification of a product in its packaging havebeen in use for as long as there have been products delivered inpackages. In the earliest days of bar codes, a “mark and space” symbolwas printed onto the packaging. Then, through use of a symbol reader(e.g., a barcode reader/scanner), a particular product could beidentified.

Printing of such symbols on packaging is very inexpensive, and symbolreaders are inexpensive enough to be deployed with, and integrated into,for example, a cash register. When such a symbol reader andcorresponding cash register are further interfaced with a centralcomputer system, purchase of a unit of a uniquely identified product canbe tallied. Inventory accounting, ordering, product replenishment, andother functions of ongoing commerce can be facilitated, in some caseswithout human intervention.

In some cases, however, it is not possible and/or not convenient toprint such bar codes onto product packaging and/or, in some cases it isnot possible or convenient to deploy a reader. In such cases, a radiofrequency identifier (RFID) can be affixed to or embedded in the productor its packaging. When the product—with its affixed or embedded RFID—isin proximity to an RFID reader, the presence can be tallied. A givenRFID can be manufactured so as to emit a unique identifier whenstimulated by a “ping”. The unique identifier can have any number ofbits, and as such the unique identifier can be associated with aparticular product. As such, product replenishment and other functionsof commerce can be facilitated.

Unfortunately, merely identifying the product, or merely identifying aparticular existence and location of the identified product, haslimitations. For example, while the sensing of a product at a cashregister or at an egress can be valuable information (e.g., to detectthe purchase of a unit of a product, or to detect movement of a unit ofa product), it is sometimes valuable to sense more information (e.g.,the state) about the particular unit of the product.

Some attempts have been made to sense characteristics of contents byprinting a sensing device on the product packaging and “pinging” thesensing device to gather information about the contents. However, suchsensing devices have been limited to measuring only environmentalvariables such as humidity, temperature, etc. Thus, the need to sensemore information (e.g., the state) about the particular unit of theproduct remains unfulfilled.

For example, it might be useful to know how full a container is. It mayalso be useful to know if a container is leaking, or if the contents aredecaying, rotting or for other reasons exuding gasses, etc. Thissituation is further complicated by the need to regularly update thestate information about a plurality of units of different products. Forexample, in a household situation, it might be desired to regularlyupdate the state information (e.g., quantity, potency, staleness, etc.)of any or all products that are encountered as a consumer traverses hisor her domicile (or car, or boat, etc.).

Neither conventional RFIDs nor conventional near-field labels are ableto provide the needed information. What is needed are systems thatfacilitate collection from new types of sensing devices that can emitnot only identification information, but also product-specific stateinformation.

DEFINITIONS AND USE OF FIGURES

Some of the terms used in this description are defined below for easyreference. The presented terms and their respective definitions are notrigidly restricted to these definitions—a term may be further defined bythe term's use within this disclosure. The term “exemplary” is usedherein to mean serving as an example, instance, or illustration. Anyaspect or design described herein as “exemplary” is not necessarily tobe construed as preferred or advantageous over other aspects or designs.Rather, use of the word exemplary is intended to present concepts in aconcrete fashion. As used in this application and the appended claims,the term “or” is intended to mean an inclusive “or” rather than anexclusive “or”. That is, unless specified otherwise, or is clear fromthe context, “X employs A or B” is intended to mean any of the naturalinclusive permutations. That is, if X employs A, X employs B, or Xemploys both A and B, then “X employs A or B” is satisfied under any ofthe foregoing instances. As used herein, at least one of A or B means atleast one of A, or at least one of B, or at least one of both A and B.In other words, this phrase is disjunctive. The articles “a” and “an” asused in this application and the appended claims should generally beconstrued to mean “one or more” unless specified otherwise or is clearfrom the context to be directed to a singular form.

Various embodiments are described herein with reference to the figures.It should be noted that the figures are not necessarily drawn to scale,and that elements of similar structures or functions are sometimesrepresented by like reference characters throughout the figures. Itshould also be noted that the figures are only intended to facilitatethe description of the disclosed embodiments—they are not representativeof an exhaustive treatment of all possible embodiments, and they are notintended to impute any limitation as to the scope of the claims. Inaddition, an illustrated embodiment need not portray all aspects oradvantages of usage in any particular environment.

An aspect or an advantage described in conjunction with a particularembodiment is not necessarily limited to that embodiment and can bepracticed in any other embodiments even if not so illustrated.References throughout this specification to “some embodiments” or “otherembodiments” refer to a particular feature, structure, material orcharacteristic described in connection with the embodiments as beingincluded in at least one embodiment. Thus, the appearance of the phrases“in some embodiments” or “in other embodiments” in various placesthroughout this specification are not necessarily referring to the sameembodiment or embodiments. The disclosed embodiments are not intended tobe limiting of the claims.

FIG. 1 depicts an environment 100 in which electromagnetic state sensingdevices disclosed herein can be deployed and configured to emit not onlyidentification information, but also product state information.Specifically, the figure is being presented with respect to itscontribution to addressing the problem of how to inexpensively deploystate sensors. More specifically, FIG. 1 depicts an environment wherebyquantitative values can be sensed by an electromagnetic state sensingdevice (EMSSD) and relayed to a computing site for data processing.“Electromagnetic” as used herein refers to signals that propagate atrelatively low frequencies (e.g., 125 kHz) or at higher radiofrequencies (13.6 MHz), or higher.

As shown, sensors 100 (e.g., sensor 101 ₁, sensor 101 ₂, and sensor 101₃) are stimulated with a ping. The stimulated sensors 100 emit aresonant signature that characterizes one or more aspects of the productthat is within its corresponding container. Several different containertypes and several different container aspects are depicted.

A ping can be raised, for instance, by a smartphone (or other type ofmobile device). Specifically, an application (“app”, i.e., a softwareapplication, computer program, computer-readable medium) on a mobiledevice (e.g., a smartphone) can control an electromagnetic emitterdevice driver (e.g., a near-field communication (NFC) device driver)which in turn can cause the electromagnetic emitter device to raise aping. As such, the frequency, duration, and shape of a ping can becontrolled. Upon excitation by a ping, a nearby sensor resonates andemits a signature that encodes information pertaining to aspects of theproduct inside its container. The information pertaining to aspects ofthe product inside its container are reformatted and relayed upstreamfor further processing. In some embodiments, and as shown, theinformation that is reformatted and relayed upstream can be routed forcommunication over the internet or intranet 108 for additional sensordata processing.

Many different types or configurations of EMSSDs can be applied toproduct packaging. As shown, a type1 EMSSD 101 ₁ can be applied to atype1 container, a type2 EMSSD 101 ₂ can be applied to a type2container, and a type3 EMSSD 101 ₃ can be applied to a type3 container.Such containers can be a vessel (e.g., a type1 container such as a jugor bottle made of plastic or glass) to hold liquids (e.g., detergents,alcohol, fuel, milk, etc.).

Alternatively, containers can be a carton (e.g., a type2 container suchas cardboard or paperboard box, which may or may not be coated with aplastic material) to hold any contents. Further, a container can be aspecialized container (e.g., a type3 container such as a pill bottle,hinged box, dropper bottle) that is designed to contain some particularproduct, such as medicine. Any of the foregoing containers might bepresented in any setting.

Strictly as one example, the foregoing containers of different typesmight be found in a household setting. Accordingly, a consumer mightwalk through his or her domicile and, during the course of walking, themobile device will emit one or more electromagnetic pings and captureelectromagnetic returns. Any one or more user devices 117 that can becontrolled to emit electromagnetic radiation can emits pings and capturereturned signals.

As depicted, a user device 117 can be a type1 mobile device 131 (e.g.,an iOS phone), or a user device 117 can be a type2 mobile device 132(e.g., an Android phone), or a user device 117 can be a stationaryinstance of an interrogator device 133 (e.g., a stationary RFID reader),such as might be located in a pantry or a medicine chest. Any of suchuser devices or variants can be configured with executable code (e.g.,an app) that controls, either directly or indirectly, an electromagneticemission device such as the shown NFC devices (user devices 117). Anynumber of user devices can be in general proximity of any EMSSD, andeach user device emits pings and captures responses. If the pings andresponses happen to occur at the same time and within close proximity toeach other, each app (e.g., app 1371, app 1372, and app 1373) canrecognize the collision and retry the pings, thus implementing acollision detection, multiple access protocol.

In the present disclosure, pings can be tuned to various frequencies forvarious purposes based on the type of product identified by the system,without need for human interaction. In the example shown, a first ping1021 is emitted at a first frequency that corresponds to a first RFIDfrequency. A first portion of the EMSSD 101 ₁ responds to the first pingwith a first return 1031 (i.e., an electromagnetic signal such as“PID1”) which encodes a value (e.g., a string of 1s and/or 0s) thatcorresponds to the product and/or container type. Given that encodedvalue, the app 1371 can determine (e.g., tune, tailor, customize)characteristics of a second ping 1022. The second return 1032 isresponsive to the second ping 1022. The second return 1032 encodesinformation about the contents of the shown container type1. The secondreturn 1032 from the EMSSD may be called a “signature.” In someembodiments, the second return 1032 is captured by the app and decodedon the mobile device. In other embodiments, the second return 1032 iscaptured by the app, packaged into network communication packets, andforwarded to cell tower 114, which in turn relays the networkcommunication packets to a data processing facility (e.g., sensor dataprocessing module 110) via the Internet. The data processing facility inturn applies rule sets 121 to determine a further action (replenishment,discard, repair, etc.).

The devices and systems shown in environment 100 operate together toform an autonomous monitoring system, such as a fulfillment system. Asshown the sensor data processing module 110 communicates over autonomousfulfillment path 1291 to a delivery service, which in turn traversesautonomous fulfillment path 1292 to deliver replenished product to theuser.

As indicated above, an EMSSD can be configured to correspond to aparticular product and/or container type. FIG. 1 depicts a carton, shownas container type2, into which the carton product can be situated.Strictly as one example, the container type2 might hold perishables(e.g., fruits, vegetables, etc.). A corresponding EMSSD can beconfigured to sense any or all of, for instance, (1) a level or volumeof product inside the container, (2) a concentration of gasses thataccompany perishable foods or food spoilage, (3) a temperature. Inoperation, a ping 1023 at an RFID frequency causes a portion of EMSSD101 ₂ to respond with return 1033 that encodes a product ID (e.g.,“PID2”). The product ID is used as an index for the rule sets 121 toisolate at least one rule 122, the application of which rule results intuning data being delivered to the app in the form of a downstreammessage 1261. For example, based on the product identified from thefirst ping, the selected rule may customize the signal frequency rangeand/or number of pings for the type of sensor on the product, to be usedwhen subsequent pings are sent to gather information about the contentsin the product packaging.

Some topologies of environment 100 include an intranet 108. In some ofsuch topologies a downstream message 1261 passes through a hub 106before being routed to the app. In such cases, the occurrence ofdetection of the product corresponding to the product ID is logged inlog 127, which log is used for various purposes, some of which arediscussed infra.

As discussed, the downstream message 1261 may contain tuning data. Thetuning data may include information used by the app to send one or morefurther pings (e.g., ping 1024). The further pings may be tuned toparticular frequencies determined based at least in part on thecharacteristics of the EMSSD. More specifically, the product ID can beused as a key to retrieve one or more rules, which in turn can informthe app about specific ping frequencies as well as the timing of pings.Strictly as one example, rules can be processed by the app so as tointerrogate an EMSSD in accordance with any of various pings, includingsimple to complex combinations of pings over any time period and invarious timed sequences. As such, the return 1034 may include severalsignatures in response to the various pings, any of which signatures canbe sent as messages (e.g., upstream message 1251, upstream message 1252)(e.g., over the internet) to the sensor data processing module 110 foranalysis. The analysis may result in determination of any or all of, forinstance, (1) a level or volume of product inside the container, (2) aconcentration of analytes that accompany perishable foods or foodspoilage (e.g., ethylene, ammonia, other gasses), (3) a temperature,and/or other information about the state of contents in the container.The determinations can be sent to the hub 106 as formatted content indownstream message 1262.

In some topologies, the downstream message 1261 passes through a hub 106before being routed to the app. A hub can be implemented by a voiceactivated command 105 (e.g., a voice assistant). The voice assistant canintercept the downstream message 1261 and process it, possibly byemitting a notification 107, which notification may be in the form ofnatural language such as “It's time to order more kale—shall I place anorder for you?” Or “It got too warm in here today—you should move thekale to a cooler location.” Or “The kale is going bad—you should compostit now.” In some topologies the notification 107 can take other formssuch as, but not limited to, text or email messages. The notificationmessage may include information such as a quantity indication, anexpiration date, a refill date, a refill count, a lot number, a chemicalcomposition, and/or a concentration indication. In some topologies, alog can be maintained of at least some of the information regardingcontents in the product packaging. For example, the log may include anentry corresponding to at least a portion of the information about thecontents. The log can be maintained by a network access point, where thenetwork access point may be activated by receiving a voice activatedcommand.

In some settings, and using all or portions of the foregoingcommunication and data analysis techniques, an interrogator device 133emits ping 1025, receives return 1035 (e.g., product ID “PID3”) and thenemits a further ping 1026, which further ping is tuned specifically forthe characteristics of container type3 and/or the characteristics of theproduct that is contained in container type3. The emission of thefurther ping 1026, results in emission of return 1036.

As mentioned hereinabove, an app on a mobile device (e.g., a smartphone)can control an electromagnetic emitter device driver (e.g., an NFCdevice driver) which in turn can cause the electromagnetic emitterdevice to raise a ping. A processing flow in one illustrative deploymentscenario is presented in FIG. 2 .

FIG. 2 presents a flow chart depicting a processing flow 200 by whichelectromagnetic state sensing devices can be deployed. As an option, oneor more variations of processing flow 200 or any aspect thereof may beimplemented in the context of the architecture and functionality of theembodiments described herein. The processing flow 200 or any aspectthereof may be implemented in any environment.

In the depicted deployment scenario, an app is developed by applicationand driver software engineers and stored at a web-accessible location(step 202). The web-accessible location 254 can be any location where adownloadable instance of an app 252 can be stored. A download can berequested by any requesting device 256 that is connected to theinternet. Moreover, the requesting device can be a mobile device of anytype, or can be a stationary device of any type such as a desktopcomputer or a hub or a digital assistant. In this scenario, therequesting device 256 is depicted as a smartphone but may also be, forexample, a smartwatch, a tablet or a laptop computer.

At any moment in time the requesting device can issue a request (e.g.,via an Internet call to a uniform resource identifier (URI)), whichrequest causes the app to be downloaded onto the device and configuredfor ongoing operation (step 204). The configuration can be specific tocharacteristics of the target device (i.e., requesting device) and/orany supervisory software (e.g., operating system) that is hosted on thetarget device.

At some moment in time after the download and configuration, the appenters a processing loop (step 206). The iterations through the loop 220can be performed on any schedule, possibly a schedule that implementsvarious power-saving techniques. In some cases, the order of theoperations performed in the loop can change based on conditions that arepresent at the moment. Although the app operations 205 depict aparticular flow of the operations, in some situations alternativeordering is possible and, in some cases, some of the operations are notperformed in a given iteration of the loop.

As shown, the loop 220 includes operations to emit a first ping signalwhen in proximity of an EMSSD (step 208) so as to stimulate at least theidentification portion 261 of the EMSSD. Based on an identification code(e.g., a product ID) derived from an identification signal (step 210),the app may apply all or portions of applicable rules (step 212). Theidentification code (e.g., a product ID) can be used as an index intothe rule sets 121 to identify EMSSD rules 209 and fulfillment rules 211.

Application of certain of the EMSSD rules 209 result in tuning databeing delivered to the app. Application of certain of the fulfillmentrules 211 result in actions associated with the product contents, suchas reading a liquid level or providing measurements of differentanalytes, or reading a quantity of contents within its container. Theapp in turn will transmit a second ping signal (step 214) so as tostimulate at least the state portion 262 of the EMSSD. The app receivesreturned state signals that are returned in response to the second pingsignal based on the state of the product at the time of the second ping(step 216). Those returned state signals are decoded to determine stateinformation. For example, the printed electromagnetic state sensingdevice may emit a first variation of the second electromagneticradiation signal (e.g., a first resonant frequency) when contents withinthe product packaging are in a first state, and emit a second variationof the second electromagnetic radiation signal (e.g., a second resonantfrequency) when contents within the product packaging are in a secondstate. In some cases, the returned state signals are analyzed by therequesting device (e.g., by the app) while in other cases, such asshown, the requesting device offloads the requesting device by sendingthe returned state signals to an upstream network device (step 218).

In this particular embodiment, the upstream device is an instance of hub106, however the upstream device can be any device connected to anintranet or connected to the internet.

The foregoing processing relies at least in part on responsecharacteristics of the EMSSD. In particular, the app relies on theaspect that an EMSSD includes identification portion 261 and at leastone state portion 262. Various techniques for forming an EMSSD are shownand discussed with reference to FIG. 3A.

FIG. 3A is a schematic of an electromagnetic state sensing device 300A.As an option, one or more variations of electromagnetic state sensingdevice 300A or any aspect thereof may be implemented in the context ofthe architecture and functionality of the embodiments described herein.The electromagnetic state sensing device 300A or any aspect thereof maybe implemented in any environment.

The EMSSD 300A is configured as an elongated sensor. That is, the EMSSD300A has a plurality of portions that span over a length (e.g.,longitudinally in a particular direction, such as vertically) wherecontents within a product are located. As shown, a first resonanceportion 301 of the EMSSD 300A is configured to provide functions of anRFID. Specifically, when pinged at a predetermined frequency, the firstresonance portion 301 energizes and emits a string of bits, at least aportion of which can be concatenated to form a unique identificationcode. The EMSSD 300A also includes a second resonance portion 302, athird resonance portion 303, and a N^(th) resonance portion 399, wherethe second through N^(th) resonance portions may be used to conveyinformation about the product (i.e., state of the contents in theproduct packaging). There may be many resonance portions juxtaposed(e.g., in a linear array, as shown) in proximity to the N^(th) resonanceportion 399. That is, the resonance portions of the EMSSD 300A arearranged along a path and may or may not be adjacent to each other.

In some implementations, the EMSSD 300A may be printed on a surface ofthe container using an ink printing process in which each of theplurality of resonance portions can be printed onto a correspondingportion of the container surface, using the ink, and configured to havea different resonance frequency than the other resonance portions. Insome aspects, the resonance frequency of a respective resonance portionof the EMSSD 300A may be determined by a material property and/orgeometry of the printed ink corresponding to the respective resonanceportion. In some aspects, the resonance portions of the EMSSD 300A maybe substantially the same size and shape, and may be printed onto thecontainer surface using different carbon-containing inks. In otheraspects, the resonance portions of the EMSSD 300A may be printed ontothe container surface using the same carbon-containing inks, and theresonance portions may have different sizes and/or geometries than oneanother. In one implementation, the identification portion 261 of theEMSSD 300A may be tuned to resonate at a different frequency orfrequencies than any state portion.

The various portions or components of the EMSSD 300A can be printed invarious geometries using carbon-containing inks. In some aspects, thegeometry (e.g., linear/curved/spiral patterns, line widths, shapefactors) and carbon-containing inks (e.g., compositions of variousallotropes) may be determined by the manufacturer or designer of theEMSSD based on sensing criteria specific to the EMSSD 300A. In somecases, the sensing criteria includes an environmental indication such as“Is ethylene present?” or “Is this portion of the EMSSD deformed frompresence of liquid?”, etc. In some cases, a sensing criterion and therespective resonance corresponds to an environmental indication such as“What is the permittivity at this location?” As such, a series ofresonant portions of an EMSSD can be printed on a container, where theseries of resonant portions are tuned to respond to the particularcontainer and contents to be detected, and/or may be tuned based on theparticular location of that resonant portion on the container. Forexample, a change in the amount of liquid contents in a container willcause a change in permittivity sensed by the EMSSD.

Accordingly, the EMSSD can be designed to be sensitive to thepermittivity of the particular resonant portion in a then-currentenvironment. Techniques to accomplish and/or tune sensitivity to thepermittivity or permeability of the particular resonant portion in athen-current environment include choosing a particular carbon ink, orcombinations of carbon inks, and tailoring geometries (e.g., layoutand/or dimensions) of electrode lines. Strictly as one example, acontainer that holds liquid will exhibit a first permittivity when thecontainer is full, whereas the same container will exhibit a secondpermittivity when the container is, for instance, nearly empty.

This phenomenon can be used when determining the level of liquid in acontainer. In fact, this phenomenon can be observed when using only asingle resonance portion (e.g., as an analog signal to a particulardegree of accuracy), or when using a series of resonance portions suchas in an elongated linear array of resonance portions (e.g., which areconfigured into a series of digital bits to any desired degree ofaccuracy). In the case of a single resonance portion, the frequencyvariance over environmental changes comprises the analog signal, whereasin the case of multiple resonance portions, the return from eachresonant portion is analyzed against a threshold to determine an “on” or“off” value. The “on” or “off” values of multiple resonance portions canbe combined to form a string of digital bits.

Although the foregoing example is specific to liquid in a container,deployment of the EMSSDs as disclosed herein can be used to detect anychange in the environment in proximity of the container. As examples ofchange in the environment, EMSSDs can detect anything that presents anyone or more of a galvanostatic change, and/or a piezo-static change,and/or a potentio-static change. Any such change or changes in theproximal environment causes a change or changes in the resonant responseor responses of one or more portions of the EMSSD. For example, apiezo-static change may result from deformation of the product contents(e.g., expansion due to temperature or quantity of contents present),which can cause strain on the resonant portions of the EMSSD andconsequently change the resonant frequency emitted. Different types ofproduct contents have different densities, and as such differentproducts can cause different degrees of strain on the resonant portions.As such, each product and each container may have a unique EMSSD, whichis calibrated for that specific product and container combination.

Techniques for sensing the level of liquid in a container are shown anddescribed in the deployment scenarios of FIG. 3B1 and FIG. 3B2.

FIG. 3B1 illustrates a deployment scenario 300B1 in which a first stateof liquid contents is measured. As an option, one or more variations ofdeployment scenario 300B1 or any aspect thereof may be implemented inthe context of the architecture and functionality of the embodimentsdescribed herein. The deployment scenario 300B1 or any aspect thereofmay be implemented in any environment.

In this deployment scenario, the EMSSD is printed on the side (e.g.,outer surface) of a liquid container. In other deployments, the EMSSD isprinted on the inside of a container. In other deployments, the EMSSD isprinted on top of a label that is affixed to a container.

When the liquid fills the container to near capacity (as shown),resonant portion 303 through resonant portion 399 overlay areas wherethere is liquid in the container, whereas resonant portion 302 is in aposition where there is no liquid in the container. The permittivityand/or permeability of the environment around the resonant portions atthose two locations are different, based at least on the level of theliquid inside the container.

Accordingly, given that other parameters are the same across the lengthof the EMSSD, the resonant frequency emitted by resonant portion 302 isdifferent from resonant portion 399. The aforementioned parametersinclude materials and environmental characteristics such as thedensities of the contents or its packaging, the dielectric constants ofthe contents or its packaging, the permeability of a label that isaffixed to packaging, the shape of the container, variations ofthickness of the container, etc.

Given the several ping returns from the several resonance portions ofthe EMSSD, the differences in the several ping returns correspond to aliquid level. More specifically, several pings at different frequenciesare emitted by the user device. These different frequencies triggerresponses in the form of ping returns from different resonant portionsof the EMSSD. The signals that comprise these ping returns are thenanalyzed to identify the amplitudes of center frequencies.

A nearly empty liquid level is shown and described in the deploymentscenario of FIG. 3B2. In some situations, the presence or absence ofliquid dominates the resonance of a particular resonant portion.However, the presence or absence of liquid at one end of the EMSSD mightcause a variation in the resonant frequency of a different resonantportion that is disposed at the opposite end of the EMSSD. This effect,as well as other effects that are brought about by the geometry of thecontainer, can be measured during calibration procedures.

Further details regarding printed sensors and resonant components aredescribed in U.S. Pat. No. 10,218,073, entitled “Antenna withFrequency-Selective Elements,” which is assigned to the assignee of thepresent application and is incorporated herein by reference.

FIG. 3B2, FIG. 3B3 and FIG. 3B4 illustrate deployment scenarios 300B2,300B3 and 300B4, respectively, in which a second state of liquidcontents is measured and optionally displayed on the container. As anoption, one or more variations of deployment scenarios 300B2, 300B3 or300B4 or any aspect thereof may be implemented in the context of thearchitecture and functionality of the embodiments described herein. Thedeployment scenarios 300B2, 300B3 or 300B4 or any aspect thereof may beimplemented in any environment.

When the liquid in the container is almost empty (as shown in FIG. 3B2),resonant portion 302 through resonant portion 398 are in a positionwhere there is no liquid in the container, whereas resonant portion 399is in a position where there is liquid in the container. Thepermittivity and/or permeability of the environment at those twolocations are different, based at least on the level of the product.Accordingly, given that other parameters are the same across the lengthof the EMSSD, the resonant frequency emitted by resonant portion 302 isdifferent from resonant portion 399. Given the several ping returns fromthe several resonance portions of the EMSSD, the differences in theseveral ping returns correspond to a liquid level. The accuracy (e.g.,full, ½ full to ±¼ full, ¼ full to ±⅛ full, etc.) can be configured intothe EMSSD, such as by the number, length and/or spacing of resonantportions.

In some embodiments, the state of the contents may be displayed on thecontainer, such as with a printed visual state indication pattern on astate display 3990 as shown in FIG. 3B3. The state display may beprinted using, for example, carbon-containing inks. In this figure, thestate display 3990 reads “FULL”, indicating that the level of liquid inthe container is full. The state display 3990 may be printed directly onthe outer surface of the container or may be printed on a substrate(e.g., a label) and affixed to the container.

Although the state display 3990 is located at the bottom end of theEMSSD in this figure, the state display 3990 may be located elsewhere inthe container, such as at the upper end of the EMSSD, or at a separatelocation from the EMSSD. The state display 3990 may be used to indicatevarious types of states of the product contents, such as quantities,freshness, or a suggested action (e.g., “time to reorder”), where theindication may utilize text and/or graphics (e.g., icons).

FIG. 3B4 shows a cross-sectional view of a printed state display 3990according to some deployment scenarios. State display 3990 is anelectrophoretic visual display device using a carbon matrix 3991 (i.e.,an electrophoretic display matrix), in accordance with some embodiments.Display 3990 includes a substrate 3992, a first electrode layer 3993 onthe substrate 3992, a layer of the carbon matrix 3991 on the substrate3992, an electrophoretic ink 3994 within carbon matrix 3991, and asecond electrode layer 3995 on the carbon matrix 3991. When theelectrode layers 3993 and 3995 are energized, ink 3994 moves toward oraway from layer 3995 to form images (e.g., patterns, graphics, text) tobe viewed from layer 3995, as indicated by the icon of an eye. Thecarbon matrix 3991 is made of carbon particles 3996 linked by polymers,forming a porous network. Substrate 3992 may be a flexible material suchas a polymer film or paper material (e.g., cardboard, paper,polymer-coated paper, and polymer films).

The thickness of the carbon matrix 3991 layer can be made thinner thanconventional electrophoretic display materials (i.e., shorter distancebetween electrode layers 3993 and 3995) because of the conductive natureof the carbon matrix 3991, which enables electrode connections withinthe matrix itself. For example, the thickness of carbon matrix 3991 maybe 10 □m to 40 □m or 10 □m to 100 □m. The electrical conductivity of thecarbon matrix 3991 may be greater than 20,000 S/m or greater than 5,000S/m or greater than 500 S/m or greater than 50 S/m. Having a thinnerimmobile phase (carbon matrix 3991) beneficially requires less energy tomove the ink 3994, making the display 3990 low-power and therefore moreamenable to being powered solely by energy harvesting methods. Forexample, the state display 3990 may be powered by an energy harvestingantenna 3997, which may harvest energy from electromagnetic signalsemitted by the user device.

Carbon matrix 3991 is a porous conductive layer with pores within orbetween carbon particles 3996 that enable ink 3994 to move through thecarbon matrix 3991. Ink that moves toward second electrode layer 3995creates a visible image, while ink that moves away from layer 3995creates blank spaces in the image that is viewed. In some embodiments,the ink 3994 may be a white electrophoretic ink to contrast the darkcolor of carbon matrix 3991.

Carbon matrix 3991 is made of carbon particles 3996 that are heldtogether by a binder, such as a polymer (e.g., cellulose, celluloseacetate butyrate, styrene butadiene, polyurethane, polyether-urethane)or cross-linkable resins (e.g., acrylates, epoxies, vinyls) that formpolymerizable covalent bonds. The binder links the carbon particles 3996together but does not encompass all of the space between the carbonparticles such that pores (i.e., spaces, voids) are present within thecarbon matrix 3991. The carbon particles 3996 are electricallyconductive and may include allotropes such as graphene, carbonnano-onions (CNOs), carbon nanotubes (CNTs), or any combination ofthese. Some or all of the carbon particles 3996 may be aggregates ofsub-particles of these allotropes. In some embodiments, a majority ofthe carbon matrix 3991 may be graphene, such as greater than 50%, orgreater than 80%, or greater than 90% of the carbon particles in thecarbon matrix 3991 being graphene. In some embodiments, the statedisplay 3990 is an electrophoretic display matrix comprising a pluralityof carbon particles cross-linked with each other by a polymer, where thematrix has a porosity comprising at least one of: i) an inter-particleporosity having an average distance of up to 10 □m between the carbonparticles, or ii) an intra-particle porosity having an average pore sizeof greater than 200 nm. Further details of printed visual displays maybe found in U.S. Provisional Patent Application No. 62/866,464, filed onJun. 25, 2019 and entitled “Electrophoretic Display”; which is owned bythe assignee of the present disclosure and is incorporated by referencein its entirety.

A technique to determine a dynamic range of sensitivity based on anumber of independent sensor portions of an EMSSD is given in FIG. 3C.

FIG. 3C is a selection chart 300C for determining a dynamic range of anelectromagnetic state sensing device. As an option, one or morevariations of selection chart 300C or any aspect thereof may beimplemented in the context of the architecture and functionality of theembodiments described herein. The selection chart 300C or any aspectthereof may be implemented in any environment.

As shown, the more sensor portions that are used in an elongated EMSSD,the more accurate the readings can be. In the figure, the dynamic rangeof 3 dB corresponds to a ratio of 2 (one bit corresponding to one sensorportion), 6 dB corresponds to a ratio of 4 (two bits corresponding totwo sensor portions), and 9 dB corresponds to a ratio of 8 (three bitscorresponding to three sensor portions). As examples, if there is onlyone independent sensor, the reading can be either {empty or full} with alarge plus or minus error, whereas if there are three sensor portions(e.g., three portions arranged with equal spacing in the direction ofhow the product contents will be depleted), the combination of readingsfrom each of the three sensors can indicate {full, ⅞, ¾, ⅝, ½, ⅜, ¼, ⅛,or empty} with a plus or minus error of approximately 1/16th. That is,the various indications will result from conditions in the environmentthat correspond to whether the product contents fully cover, orpartially cover, or do not cover the various resonant portions.

The heretofore-described embodiments rely at least in part on readingsfrom EMSSD portions, where each portion in a different environmentresponds to a ping with a different respective return signature. Thedifferent respective return signatures can be measured within variousenvironments, and the readings of the return signatures can be used ascalibration points as shown in FIG. 4A1 and FIG. 4A2.

FIG. 4A1 and FIG. 4A2 are equivalent circuit models 400A1 and 400A2,respectively, of an electromagnetic state sensing device in a firstenvironment (e.g., carton nearly full of powder) and a secondenvironment (e.g., carton almost empty). As an option, one or morevariations of the equivalent circuit models or any aspect thereof may beimplemented in the context of the architecture and functionality of theembodiments described herein. The equivalent circuit models or anyaspect thereof may be implemented in any environment.

In exemplary embodiments, each carbon-containing material (i.e., ink)used in each portion of an EMSSD is formulated differently so as toresonate at different tuned frequencies. The physical phenomenon ofmaterial resonation can be described with respect to a correspondingmolecular and/or morphological composition. Specifically, a materialhaving a first molecular structure will resonate at a first frequencywhen in a particular environment, whereas a material having a second,different molecular structure will resonate at a second, differentfrequency in the same particular environment. Similarly, a materialhaving a first molecular structure will resonate at a first frequency orfrequencies when in a particular environment, whereas the same materialhaving the same molecular structure will resonate at a second, differentfrequency or frequencies when in a different environment. In many cases,the aforementioned resonant frequencies form a signature that is uniqueto the composition when situated in a particular environment. Forexample, a first carbon-containing ink may be formulated primarily withgraphene. A second carbon-containing ink may be similar to the first inkbut differ in molecular structure from the first carbon-containing ink,such as having a different composition (e.g., having multi-walledspherical fullerenes or other allotrope added) or structure (e.g.,graphene made of fewer or more layers than in the first ink).

This phenomenon is controllable using the herein described techniques.More particularly, (1) the material can be tuned to resonate innately ata selected frequency, and (2) the response of the material in differentenvironments can be measured and used in calibration.

As shown in FIGS. 4A1 and 4A2, and as discussed hereunder, thedifference between a first ping return measurement from a first resonantportion in first environment compared to a second ping returnmeasurement from the same resonant portion in a second environmentcorresponds to the difference in a resonant frequency. Furthermore,other parameters being equal, the difference between a first environmentand a second environment can correspond to a product sensing state(e.g., product is present or product is not present). The difference ina resonant frequency between product sensing states (e.g., state=productpresent or state=product not present) can be measured in situ. In somecases, the difference in a resonant frequency between product sensingstates can be calculated. Regardless of if the difference in a resonantfrequency between product sensing states is empirically measured (e.g.,for calibration) or if the difference in a resonant frequency betweenproduct sensing states is calculated, the phenomenon arises due toatomic structure or molecular structure of materials in the sensor,and/or due to environmental conditions present at the time ofmeasurement. The following paragraphs explain this phenomenon, step bystep.

As is known in the art, atoms emit electromagnetic radiation at anatural frequency for the particular element. That is, an atom of aparticular element has a natural frequency that corresponds to thecharacteristics of the makeup of the atom. For example, when a Cesiumatom is stimulated, a valence electron jumps from a lower energy state(e.g., a ground state) to a higher energy state (e.g., an excited energystate). When the electron returns to its lower energy state, it emitselectromagnetic radiation in the form of aphoton. For Cesium, the photonemitted is in the microwave frequency range of 9.192631770 THz.

Structures that are larger than atoms, such as molecules formed ofmultiple atoms, also resonate (i.e., emit electromagnetic radiation) atpredictable frequencies. For example, liquid water in bulk resonates at109.6 THz. Water that is in tension (e.g., at the surface of bulk, invarious states of surface tension) resonates at or near 112.6 THz.

Carbon atoms and carbon structures also exhibit natural frequencies thatare dependent on the structure. For example, the natural resonantfrequency of a carbon nanotube (CNT) is dependent on the tube diameterand length of the CNT. Growing a CNT under controlled conditions (e.g.,to control the tube diameter and length) leads to controlling thestructure's natural resonant frequency. Accordingly, growing CNTs is oneway to tune to a desired resonant frequency.

Other structures formed of carbon can be created under controlledconditions. Such structures include but are not limited to carbonnano-onions (CNOs), carbon lattices, graphene, graphene-based, othercarbon containing materials, engineered nanoscale structures, etc.and/or combinations thereof. Such structures can be formed so as toresonate at a particular tuned frequency and/or such structures can bemodified in post-processing so as to obtain a desired characteristic orproperty. For example, a desired property such as a high reinforcementvalue when mixed with a polymer can be brought about by the selectionof, and ratios of particular combinations of, materials and/or by theaddition of other materials.

Moreover, co-location of multiples of such structures introduces furtherresonance effects. For example, two sheets of graphene may resonatebetween themselves at a frequency that is dependent on the length,width, spacing, shape of the spacing, and/or other physicalcharacteristics of the sheets and/or their juxtaposition to each other.

The aforementioned materials have specific, measurable characteristics.This is true for naturally occurring materials as well as for engineeredcarbon allotropes. Such engineered carbon allotropes can be tuned toexhibit physical characteristics. For example, carbon allotropes can beengineered to exhibit physical characteristics corresponding to (a) aparticular configuration of constituent primary particles, (b) formationof aggregates, and (c) formation of agglomerates. Each of these physicalcharacteristics influence the particular resonant frequencies ofmaterials formed using corresponding particular carbon allotropes.

In addition to tuning a particular carbon-based structure for aparticular physical configuration that corresponds to a particularresonant frequency, carbon-containing compounds can be tuned to aparticular resonant frequency or set of resonant frequencies. A set ofresonant frequencies is termed a ‘resonance profile’. One possibletechnique for tuning a particular carbon-based structure to emit set ofresonant frequencies is disclosed as follows.

Forming Frequency-Tuned Materials

Carbon-containing resonance materials can be tuned to exhibit aparticular resonance profile by tailoring the specific compounds thatmake up the materials to have particular electrical impedances.Different electrical impedances in turn correspond to differentfrequency response profiles.

Impedance describes how difficult it is for an alternating current toflow through an element. In the frequency domain, impedance is a complexnumber having a real component and an imaginary component due to thestructures behaving as inductors. The imaginary component is aninductive reactance component XL, which is based on the frequency f andthe inductance L of a particular structure in Eq. 1:XL=2πfL  (Eq. 1)

As the received frequency increases, the reactance also increases suchthat, at a certain frequency threshold, the resonant response willattenuate. Inductance L is affected by the electrical impedance Z of amaterial, where Z is related to the material properties of permeability□ and permittivity □ by the relationship in Eq. 2:

$Z = {\sqrt{\frac{µ^{\prime} = {jµ^{''}}}{\mathcal{E}^{\prime} + {j\mathcal{E}^{''}}}} = \sqrt{\frac{µ_{0}}{\mathcal{E}_{0}}}}$

Thus, tuning of material properties changes the electrical impedance Z,which affects the inductance L and consequently affects the reactanceXL.

The present embodiments observe that carbon-containing structures withdifferent inductances will have different frequency responses. That is,a carbon-containing structure with a high inductance L (being based onelectrical impedance Z) will reach a certain reactance at a lowerfrequency than another carbon-containing structure with a lowerinductance.

Further, the present embodiments utilize material properties ofpermeability, permittivity and conductivity when formulating acarbon-containing compound to be tuned in accordance with requirementsof a particular product state sensor.

It is observed that a first carbon-containing structure will resonate ata first frequency, whereas that same structure will resonate at a secondfrequency when that structure is in a different environment (e.g., whenthe carbon-containing structures are in physical contact with structuresof the environment).

As shown, the resonant frequency can be correlated to an equivalentelectrical circuit comprising a capacitor C₁ and an inductor L₁. Thefrequency f₁ is given by Eq. 3:

$f_{1} = \frac{1}{2\pi\sqrt{L_{1}C_{1}}}$

If the environment is changed slightly, such as when liquid in acontainer is no longer contacting the sensor or is no longer beingadjacent to the wall of the container on which the sensor is attached,then the environmental change in turn changes the inductance and/orcapacitance of the structure as a whole. The changes can be correlatedto an equivalent electrical circuit comprising a capacitor C₂ and aninductor L₂. The frequency f2 is given by Eq. 4:

$f_{2} = \frac{1}{2\pi\sqrt{L_{2}C_{2}}}$

Since the quantity f₁-f₂ is used when comparing two readings, or whencomparing a reading to a calibration point, the magnitude of thequantity f₁-f₂ determines the sensitivity. Accordingly, the geometry ofthe printed portions of an EMSSD (e.g., the length of electrical conduitlines, the width of electrical conduit lines, curvature, etc.) and thechoice of carbons used in the carbon-containing inks are often dominantfactors when determining sensitivity of an EMSSD. Even though theresonant frequency of a portion of an EMSSD can be calculated (e.g.,using the foregoing equations) many deployment scenarios rely onempirical data capture techniques to form calibration points. In manycases, the more calibration points that are taken, the more accurate arethe measurements. In various calibration scenarios, many sets ofcalibration points are taken and saved for each variation of a containerand/or intended contents.

FIG. 4B depicts an empirical data capture technique 400B as used forcalibrating electromagnetic state sensing devices in differentenvironments. As an option, one or more variations of empirical datacapture technique 400B or any aspect thereof may be implemented in thecontext of the architecture and functionality of the embodimentsdescribed herein. The empirical data capture technique 400B or anyaspect thereof may be implemented in any environment.

Practical uses of this empirical data capture technique result incapture of the actual measurements of each particular portion of amulti-portion EMSSD. In an example use scenario, a three-column tablesuch as is depicted in FIG. 4B is constructed by taking a series ofempirical measurements. Specifically, for each independent portion of anEMSSD, its response to stimulus is measured under two differentenvironmental conditions. The empirical response of a particularly-tunedindependent portion of an EMSSD is measured in a first environment(denoted R_(ENV1)) and recorded. Next, the empirical response of aparticularly-tuned independent portion of an EMSSD is measured in asecond environment (denoted R_(ENV2)) and recorded. Strictly asexamples, the first environment might be when a container is full oralmost full and the second environment might be when a container isempty or almost empty.

As can be seen R_(ENV1) is a function of two dominant variables: (1) thepermeability of the material that forms the independent portion of theEMSSD, and (2) the permittivity of the local environment. Such in situmeasurements are taken for the first environment and for the secondenvironment for each independent portion.

When an EMSSD is composed of a large number of independent portions(e.g., portion ID #2 302, portion ID #3 303, portion ID #99 399, etc.),a very accurate assessment of the contents can be made. The depiction ofFIG. 4B includes empirical measurement scenarios 460, namely astate_(FULL) scenario 461 a state_(NearEmpty) scenario 462, and astate_(Half) scenario 463. In this example, environment 1 corresponds toa set of conditions when the container is full, whereas environment 2corresponds to a set of conditions when the container is empty. Thus, ina situation where the container is completely full, each independentportion of an EMSSD resonates with a response corresponding to R_(ENV1).For comparison, in a situation where the container is near empty, eachindependent portion of an EMSSD resonates with a response correspondingto R_(ENV2), except the ‘bottom’ portion (portion ID #99), whichresonates with a response corresponding to R_(ENV1) due to some contentsremaining near the bottom portion #99.

In the situation where (1) there are just four independent portions ofan EMSSD distributed in a vertical stacking across the container (e.g.,extending from an upper to a lower portion of a container to detect aquantity of the contents in the container), and (2) the ‘top two’portions resonate with a response corresponding to R_(ENV1), and (3) the‘bottom two’ portions resonate with a response corresponding toR_(ENV2), it can be deemed that the container is at half capacity.

Some embodiments may include tuning the different carbon-containing inksto resonate at different center frequencies that are widely separated inthe frequency domain. In this way, the ping frequencies that are used tostimulate particular independent portions might also be widelyseparated. Multiple independent portions of an EMSSD can be stimulatedsuccessively using a ‘chirp’ technique, where successive pings atdifferent frequencies are separated across time slices such that theresponse signature from a given independent portion of an EMSSD is at amuch higher amplitude than any harmonic responses from other portions ofthe EMSSD. One possible signature capture technique is shown anddescribed as pertains to FIG. 5A.

FIG. 5A depicts a signature capture technique 500A as used forelectromagnetic state sensing. As an option, one or more variations ofsignature capture technique 500A or any aspect thereof may beimplemented in the context of the architecture and functionality of theembodiments described herein. The signature capture technique 500A orany aspect thereof may be implemented in any environment.

FIG. 5A is being presented with respect to a technique for capturing andanalyzing a returned signal signature after independent portions of anEMSSD formed of carbon-containing tuned resonance materials have beenstimulated by chirp signals. Specifically, the figure depictsmeasurements 550 that are taken from EMSSDs on a nearby container. As aresult of stimulation of the EMSSDs with a chirp signal sequence, theEMSSDs respond (e.g., via resonance emissions). A return response (e.g.,return signals 5121, return signals 5122) is captured from each EMSSD.More specifically, when a first EMSSD 5041 on the container isstimulated by a ping (e.g., a ping from a chirp sequence of chirpsignals 5101), return signals 5121 are received and processed.Similarly, when a second EMSSD 5042 on the container is stimulated by aping (e.g., a ping from a chirp sequence of chirp signals 5102), returnsignals 5122 are received and processed.

As shown, a particular container might include multiple EMSSDs, eachwith its respective identification portion and state portion, as well asa separate RFID. As an example, a container might be in the form of adispenser (e.g., an inhaler) for dispensing a medicament (e.g., forasthma treatment), and the dispenser might have its own RFID, separatefrom any EMSSD. The RFID might have been applied to the dispenser at thetime of manufacture of the dispenser, such as for product identificationor inventory purposes. The EMSSDs might have been applied, possiblyusing an adhesive label, by a compounder or pharmacy at the time offulfilling a prescription for the medicament, such as to track quantityand dosing information for a specific patient. For various reasons, theidentification portion of the EMSSDs might be configured to operate atdifferent frequencies. As an example, the identification portion of afirst EMSSD might operate at 125 kHz, whereas the identification portionof a second EMSSD might operate at 13.6 MHz, and so on.

The foregoing chirp/ping signals can be sent by transceiver 514. Also,the return signals can be received by the same (or different)transceiver 514. As shown, the chirp signals can occur in a repeatingsequence of chirps (e.g., chirp signals 5101, chirp signals 5102). Forexample, a chirp signal sequence might be managed by a ping control unit516 that repeats a pattern comprising a 1 GHz ping, followed by a 2 GHzping, followed by a 3 GHz ping, and so on. The entire chirp sequence canbe repeated in its entirety continuously. In some cases, there can bebrief periods between each ping such that the returned signals from theresonant materials (return signals 5121, return signals 5122) can beanalyzed (e.g., in a signature analysis module 554) immediately afterthe end of a ping. In other cases, the signals corresponding to the pingstimulus and the signals of the returned response are concurrent. Thetransceiver 514, ping control unit 516 and signature analysis module can554 may all be within a user device and software application on the userdevice (e.g., mobile or stationary device), or may be distributed onmultiple devices such as the user device and a server that is incommunication with the user device. Using digital signal processingtechniques, the signals of the returned response can be distinguishedfrom the ping signals. For example, in situations where the returnedresponse comprises energy across many different frequencies (e.g.,overtones, sidelobes, etc.), a notch filter can be used to filter outthe frequency of the stimulus.

In cases where a single container hosts two or more EMSSDs, eachindividual EMSSD may be tuned to emit different resonant responses underdifferent environmental conditions. For example, some EMSSDs are tunedto respond to changes in the contents of the container, whereas otherEMSSDs are tuned to respond to the presence of particulates or gassesthe environment.

For detecting the presence of gasses, an EMSSD is configured to comprisea sensing material (e.g., a redox mediator) that is sensitive to ananalyte such that when the EMSSD is exposed to the analyte, thecapacitance one or more of the constituent elements of the EMSSDchanges. As such, a return response in the presence of an analyte isdifferent than when in the absence of the analyte. More specifically, itcan happen that the permittivity and/or permeability of the sensingmaterial changes upon exposure to the analyte, which in turn changescapacitance of one or more constituent elements of the EMSSD (e.g., acapacitive element), which in turn indicates the presence of theanalyte.

Further details regarding general approaches to sensing an analyte aredescribed in U.S. Pat. No. 10,502,705 entitled “RESONANT GAS SENSOR,”which is hereby incorporated by reference in its entirety.

FIG. 5B depicts a signature analysis technique 500B as used forelectromagnetic state sensing. As an option, one or more variations ofsignature analysis technique 500B or any aspect thereof may beimplemented in the context of the architecture and functionality of theembodiments described herein. The signature analysis technique 500B orany aspect thereof may be implemented in any environment.

FIG. 5B illustrates aspects pertaining to sensing devices that can emitnot only identification information, but also product state information.In many situations, including the situation shown and described in FIG.5B, product state information is determined based on measurements thatare compared to predetermined points.

As shown, the flow of the system commences at step 570. A ping signal ofa selected ping frequency is transmitted by ping control unit 516. Theping signal generation mechanism and the ping signal transmissionmechanism can use any known techniques.

Strictly as one example, a transmitter module can generate a selectedfrequency (e.g., 3 GHz) and radiate that signal using an antenna ormultiple antennae. The design and location of the tuned antenna cancorrespond to any tuned antenna geometry and/or material and/or locationsuch that the strength of the ping is sufficient to energize a nearbyEMSSD and/or to induce resonance in nearby EMSSDs. In some embodiments,several tuned antennae are disposed upon or within structural membersthat are in proximity to corresponding EMSSD. As such, when an EMSSD isstimulated by a ping, it resonates back with a signature. That signaturecan be received (step 574) and stored in a dataset comprising receivedsignatures 576. A sequence of transmission of a ping, followed byreception of a signature, can be repeated in a loop.

For example, and as shown, the ping frequency is changed (step 572) inthe course of iterative passes (i.e., see “Yes” branch of decision 580).As step 574 is performed and received signatures 576 are processed, afirst signature 5781, a second signature 5782, an N^(th) signature 578N,etc. are stored. The number of iterations can be controlled by decision580. When the “No” branch of decision 580 is taken (e.g., when there areno further additional pings to transmit), then the received signaturescan be provided to a digital signal processing module (step 582) in thesignature analysis module 554. The digital signal processing moduleclassifies the signatures (step 584) against a set of calibration points586. The calibrations points might correspond to particular pingfrequencies and/or the calibrations points might correspond toparticular signatures that had been measured within an in-situenvironment. For example, a first calibration point 5881 mightcharacterize a first returned signature that would be classified asbeing indicative of a ‘full’ state of the medicament in the dispenser, asecond calibration point 5882 might characterize a second returnsignature that would be classified as being indicative of a ‘half full’state of the medicament in the dispenser, and so on for N calibrationpoints.

At step 590, classified signals are sent to an upstream network device.In some embodiments, the classified signals are relayed by a network hubthat in turn transmits the classified signals to an upstream repositorythat hosts a machine learning database. Such a machine learning databasecan be trained such that a given set of sensed measurements can becorrelated to particular product state conditions.

FIG. 6 depicts a virtual assistant 600 as used as a hub 106 in areplenishment system. As an option, one or more variations of virtualassistant 600 or any aspect thereof may be implemented in the context ofthe architecture and functionality of the embodiments described herein.The virtual assistant 600 or any aspect thereof may be implemented inany environment.

Referring again to FIG. 1 , a hub 106 can be any device that implementsnetworking communications. In some cases, a hub includes a capabilityfor natural language communication with a human user. In the exampleshown, the hub 106 is implemented by a virtual assistant. A virtualassistant can be any device such as are exemplified by devices known as“AMAZON ECHO®”, “GOOGLE HOME®”, “NEST HUB™”, etc. As used herein, avirtual assistant is any device that is (1) network connected, and (2)is capable of carrying out natural language communication with a humanuser using a voice input transducer (e.g., a microphone) and a voiceoutput transducer (e.g., speakers).

When used within an environment such as depicted in FIG. 1 , a virtualassistant can facilitate replenishment based on EMSSD readings combinedwith results of a natural language conversation. In one scenario, anEMSSD reading indicates that a perishable product has reached itsexpiration date. The digital assistant might speak a voice interactionof “The kale is going bad—do you want to re-order now?” In such ascenario, the user might answer with an audible “Yes”, which would causethe virtual assistant to transmit one or more upstream messages 125(e.g., possibly including user credentials), which upstream messagesmight include a replenishment order 620. Operational elements (e.g.,servers) that are upstream from the digital assistant might thentransmit downstream messages 126, which downstream messages mightinclude a replenishment status 622.

In some cases, such as when used within an environment such as depictedin FIG. 1 , a virtual assistant can facilitate processing of signalsemitted by EMSSDs. In particular, a virtual assistant can carry outcommunications with type1 mobile device 131 and/or a type2 mobile device132 and/or an interrogator device 133. Such communications can becarried out using the NFC unit 602 (FIG. 6 ) of the virtual assistant,or the Bluetooth low energy (BLE) unit 604 of the virtual assistant, orthe Wi-Fi unit 606 of the virtual assistant.

Furthermore, any of a variety of protocols can be implemented such thatany operations needed for product identification, and/or for productstate sensing, and/or for application of rules can be carried out in anycombination by a mobile device, and/or an interrogator device, and/or avirtual assistant, and/or any other network-connected device.

The following figures pertain to techniques for forming and executingrules serve to present a logical flow of operations. As hereinaboveindicated, processing that corresponds to application of any rule orportion thereof and/or processing that corresponds to performance of anyindividual operation can be carried out at any operational element.

FIG. 7A presents a rule codification technique 700A as used in areplenishment system based on electromagnetic state sensing devices. Asan option, one or more variations of rule codification technique 700A orany aspect thereof may be implemented in the context of the architectureand functionality of the embodiments described herein. The rulecodification technique 700A or any aspect thereof may be implemented inany environment.

As can be readily understood based on the foregoing, since there aremany products that might be situated in a given setting (e.g., in adomicile, or car, or boat, etc.) and inasmuch as the foregoing EMSSDsmay be applied to many different types of products that have manydifferent types of states, and many different states within a particularstate type, it follows that determination of the state or states of aparticular product can be facilitated by specific processing based onthe product identification. For example, if, as a result of a ping tothe identification portion of an EMSSD, the product can be identified asa 64-ounce bottle of detergent of a particular brand, then theparticular configuration of the remaining portions of the EMSSD can beknown by a lookup in a database. For example, data returned from alookup in a database might indicate that the EMSSD configuration forthat product and its particular container (i.e., the 64-ounce bottle ofdetergent) comprises eight different resonance portions that areresponsive to eight different stimulation frequencies.

Furthermore, data returned from a lookup in a database might indicatethat the EMSSD configuration for that product and its particularcontainer (i.e., the 64-ounce bottle of detergent) comprises 32different calibration points. As such, once the product has beenidentified, a great deal of information about the EMSSD configurationcan be known. Moreover, once the product has been identified, furthersteps to perform for the purpose of product state can be identified. Theflow as depicted in FIG. 7A implements a rule codification techniquesuch that any rule can be delivered to any device for execution.

As shown, the flow is initiated by event 701, which event might arisefrom an app on a user device such as a smartphone. The user deviceresponds to the event by emitting a ping frequency (step 702). Theparticular frequency of the ping can be initially known from a pingfrequency table 720, which table is implemented as a data structureaccessible to the user device. As a result of the outgoing ping orpings, at least one identification signal 703 is emitted from an RFID oran identification portion of an EMSSD. The identification signal 703 isreceived (step 704), which identification signal is converted into abinary representation (step 706) using any known signal processingtechniques. This binary representation is used to look up one or morerules (step 708) from one or more rule sets 121. The one or more rulescan be stored using any storage device at any location and can beretrieved by using any known methods for inter-device communication. Inmany cases, the one or more rules comprise information pertaining to (1)the corresponding EMSSD type, (2) the location of calibration points,(3) thresholds, and (4) additional ping instructions.

Each rule can be codified by looking up data corresponding to operandsof a rule (step 710) and by looking up operations to apply to theoperands of the rule (step 712).

Strictly as one example, a rule might indicate to “Retry if error >T”.Step 710 can look up “T” to determine a numeric value of, for example,50%. Step 712 can look up details pertaining to the operation of“Retry”, which might include, for example, a time duration to waitbefore a retry. In some cases, numeric values for operands aredetermined on the particular platform where the rule is to be executed.

When the rules have been processed through step 710 and step 712, theflow emits platform-independent rule representations 715, which are thentransmitted to a device (e.g., hub or smartphone) for execution.

FIG. 7B presents a rule execution technique 700B as used in areplenishment system based on electromagnetic state sensing devices. Asan option, one or more variations of rule execution technique 700B orany aspect thereof may be implemented in the context of the architectureand functionality of the embodiments described herein. The ruleexecution technique 700B or any aspect thereof may be implemented in anyenvironment.

As shown, the rule execution technique 700B is initiated when the device(e.g., hub or smartphone) receives the platform-independent rulerepresentations (step 752). Each individual one of theplatform-independent rule representations are decoded (step 754) todetermine a corresponding entry point on the device. Also, each of theplatform-independent rule representations are decoded to identifyoperands (step 756). A formatting table 757 might be employed to converta particular platform-independent operand representation into aplatform-specific operand representation. Then, for each entry point,the operands are formatted to correspond to the computer hardware andsoftware architecture of the platform (step 758) and theplatform-independent rule is executed on the device (step 760). In somecases, an operand might not be decoded into a numeric representation,but rather the operand is decoded into a further entry point orsubroutine. As an example, the operand “sweep” as depicted in formattingtable 757 might refer to a subroutine that covers many ranges in afrequency sweeping operation.

FIG. 8 depicts an example protocol 800 as used in a replenishment systembased on electromagnetic state sensing devices. As an option, one ormore variations of protocol 800 or any aspect thereof may be implementedin the context of the architecture and functionality of the embodimentsdescribed herein. The protocol 800 or any aspect thereof may beimplemented in any environment.

The shown protocol involved four devices: (1) a proximal EMSSD 801, (2)a user device 802, (3) a network hub 803, and (4) an upstream processingunit 804. As shown, the protocol is initiated by a user device.Specifically, user device 802 emits a first ping (emission 806). Theenergy from the first ping causes a proximal EMSSD 801 to emit a signal(emission 807), which signal includes a portion that is interpreted asan identification signal (emission 808). The identification signal isdecoded into a product ID (operation 810), which identification signalis sent to the network hub (message 812).

The network hub 803 performs a first local processing (operation 814) toprocess all or part of emission 807, then sends all or part of emission807 to upstream processing unit 804 (payload message 816). The upstreamprocessing unit 804 (i.e., upstream computing device, which may include,for example, an interrogator device having an RFID reader) accessesEMSSD rules from rules set 121 and performs first upstream processing818. The EMSSD rules are encoded as platform-independent rules and sentto the network hub (message 820), which then relays all or part of theplatform-independent rules (message 822) to the user device.

At this point in the protocol, the user device has sufficientinformation about the characteristics of the proximal EMSSD (e.g.,resulting from processing of message by determining second through Nthping signal characteristics 824) such that the state portion of theEMSSD can be interrogated by pinging any one or more resonant portionsof the proximal EMSSD. In this protocol, only one second ping (emission826) is shown, however in most cases there are many resonant portions ofthe proximal EMSSD, any or all of which portions are interrogated (e.g.,in a succession) by the user device.

Responsive to the second ping, the resonant portion of the proximalEMSSD resonates (emission 828) in a manner that emits a state signal(emission 830). The state signal is processed at the user device byapplying one or more rules (operation 832). In this embodiment, all orportions of the state signal and/or any derivatives from processing ofthe state signal are sent to the network hub (message 834), whichperforms second local processing (operation 836). The second localprocessing includes forming a payload for messages that are sent to theupstream processing unit (message 838). The upstream processing unit inturn performs second upstream processing 842.

At this point in the protocol, at least the upstream processing unit hasinformation about the particular state of a particular unit of aparticular product. As such, the upstream processing unit can availitself of additional rules that pertain to fulfillment. For example, afulfillment rule might carry the semantics of “Ask the user if anotherunit of this product should be ordered now.” Such additional rules arerelayed (message 844) to the network hub for further processing. In somecases, and as shown, the network hub will relay all or part of theadditional rules (message 846) to the user device.

Such additional rules at the user device might include forming andpresenting a confirmation question in a user interface of the userdevice. In some cases, there are several additional rules that areapplied (operation 847) at the user device. A user response, for example“Yes—order now.” might be sent to the network hub (message 848) forfurther processing and/or for relaying the response or portion thereofto the upstream processing unit (message 850). The upstream processingunit may then complete steps (operation 852) to accomplish theuser-confirmed fulfillment request.

As a result of product state determination using an EMSSD, the user wasnotified of an underlying need for replenishment. The user's desire forreplenishment was confirmed, after which replenishment was initiated. Insome cases, a fulfillment rule authorized initiation of fulfillment evenin the absence of an explicit user confirmation.

ADDITIONAL PRACTICAL APPLICATION EXAMPLES

FIG. 9 depicts a system 900 as an arrangement of computing modules thatare interconnected so as to operate cooperatively to implement certainof the herein-disclosed embodiments. This and other embodiments presentparticular arrangements of elements that, individually or as combined,serve to form improved technological processes that address how toinexpensively deploy state sensors. The partitioning of system 900 ismerely illustrative and other partitions are possible. As an option, thesystem 900 may be implemented in the context of the architecture andfunctionality of the embodiments described herein. Of course, however,the system 900 or any operation therein may be carried out in anydesired environment.

The system 900 comprises at least one processor and at least one memory,the memory serving to store program instructions corresponding to theoperations of the system. As shown, an operation can be implemented inwhole or in part using program instructions accessible by a module. Themodules are connected to a communication path 905, and any operation cancommunicate with any other operations over communication path 905. Themodules of the system can, individually or in combination, performmethod operations within system 900. Any operations performed withinsystem 900 may be performed in any order unless as may be specified inthe claims.

The shown embodiment implements a portion of a computer system,presented as system 900, and includes one or more processors that canexecute one or more sets of instructions, machine-readable code,software programs, and the like. In various implementations, executionof the instructions, machine-readable code, and/or software programs maycause the system 900 to perform one or more operations. In someimplementations, the one or more operations may include responding to arequest from a user device to download an app, for example, by receivingthe request from the user device and providing access to the app inresponse to the request, where the application is configured to causethe user device to perform a sequence of steps (module 920). The one ormore operations may include transmitting, from the user device, a firstelectromagnetic radiation ping (module 930). The one or more operationsmay include receiving, from an electromagnetic state sensing device(EMSSD) that is affixed to the product packaging, a firstelectromagnetic radiation return signal. In some aspects, the firstelectromagnetic radiation return signal is transduced by theelectromagnetic state sensing device in response to the firstelectromagnetic radiation ping.

In some implementations, transducing the first electromagnetic radiationreturn signal may produce an electromagnetic radiation signal thatencodes at least first information comprising a product identificationcode (module 940). The method may also include applying a rule that isselected based at least in part on the product identification code(module 950), and transmitting a second electromagnetic radiation pingin response to application of the rule, such as where the secondelectromagnetic radiation ping is tuned based on the rule (module 960).The method may also include receiving, from the electromagnetic statesensing device, a second electromagnetic radiation return signal thatencodes second information pertaining to the contents within the productpackaging (module 970), and sending, from the user device, at least aportion of the second information to an upstream computing device(module 980). In some aspects, the user device may be, for example, asmartphone, and may optionally include a stationary RFID reader.

In some embodiments, the electromagnetic state sensing device is aprinted electromagnetic state sensing device, which may include a firstcarbon-containing ink and optionally a second carbon-containing ink. Theprinted electromagnetic state sensing device may emit a first variationof the second electromagnetic radiation signal (i.e., a first returnsignal) when contents within the product packaging are at a first state,and the printed electromagnetic state sensing device may emit a secondvariation of the second electromagnetic radiation signal (i.e., a secondreturn signal) when contents within the product packaging are at asecond state. In some embodiments, the printed electromagnetic statesensing device may be printed longitudinally on the product packaging.

In some embodiments, the electromagnetic radiation return signal hasenergy distributed across a plurality of frequencies and is emitted bythe user device, wherein the user device is a mobile device. Theelectromagnetic radiation return signals may be emitted by anelectromagnetic emission device of a mobile device or by anelectromagnetic emission device of a stationary device. Strictly as oneexample, the electromagnetic emission device may be a near fieldcommunication device.

In some embodiments, the application is further configured to place areplenishment order in response to the second information pertaining tothe contents within the product packaging. In some embodiments, theapplication is further configured to send a notification message inresponse to the second information pertaining to the contents within theproduct packaging. The notification message may include at least one ofa quantity indication, an expiration date, a refill date, a refillcount, a lot number, a chemical composition, and a concentrationindication.

In some embodiments, the application is further configured to maintain alog of at least some of the second information pertaining to thecontents within the product packaging. The log may be maintained by anetwork access point, where the network access point may receive a voiceactivated command. The log may include an entry corresponding to atleast a portion of the second information.

In some embodiments, the application is further configured to receive,from a second electromagnetic state sensing device (EMSSD) that isaffixed to product packaging, an electromagnetic radiation relay signal,wherein the electromagnetic radiation relay signal is transduced by thesecond electromagnetic state sensing device.

Variations of the foregoing may include more or fewer of the shownmodules. Certain variations may perform more or fewer (or different)steps and/or certain variations may use data elements in more, or infewer, or in different operations.

Still further, some embodiments include variations in the operationsperformed, and some embodiments include variations of aspects of thedata elements used in the operations.

FIG. 10A through FIG. 10Y depict structured carbons, various carbonnanoparticles, and various carbon-containing aggregates, and variousthree-dimensional carbon-containing structures that are grown over othermaterials, according to some embodiments of the present disclosure.

Some embodiments of EMSSDs use carbon nanoparticles and aggregates incertain configurations. In some embodiments, the carbon nanoparticlesand aggregates are characterized by a high “uniformity” (i.e., high massfraction of desired carbon allotropes), a high degree of “order” (i.e.,low concentration of defects), and/or a high degree of “purity” (i.e.,low concentration of elemental impurities), in contrast to the loweruniformity, less ordered, and lower purity particles achievable withconventional systems and methods. This results in a high degree oftunability of the resonating portions of EMSSDs.

In some embodiments, the nanoparticles produced using the methodsdescribed herein contain multi-walled spherical fullerenes (MWSFs) orconnected MWSFs and have a high uniformity (e.g., a ratio of graphene toMWSF from 20% to 80%), a high degree of order (e.g., a Raman signaturewith an ID/IG ratio from 0.95 to 1.05), and a high degree of purity(e.g., the ratio of carbon to other elements (other than hydrogen) isgreater than 99.9%). In some embodiments, the nanoparticles producedusing the methods described herein contain MWSFs or connected MWSFs, andthe MWSFs do not contain a core composed of impurity elements other thancarbon. In some cases, the particles produced using the methodsdescribed herein are aggregates containing the nanoparticles describedabove with large diameters (e.g., greater than 10 μm across).

Conventional methods have been used to produce particles containingmulti-walled spherical fullerenes with a high degree of order, but theconventional methods lead to carbon products with a variety ofshortcomings. For example, high temperature synthesis techniques lead toparticles with a mixture of many carbon allotropes and therefore lowuniformity (e.g., less than 20% fullerenes to other carbon allotropes)and/or small particle sizes (e.g., less than 1 μm, or less than 100 nmin some cases). Methods using catalysts lead to products including thecatalyst elements and therefore have low purity (e.g., less than 95%carbon to other elements) as well. These undesirable properties alsooften lead to undesirable electrical properties of the resulting carbonparticles (e.g., electrical conductivity of less than 1000 S/m).

In some embodiments, the carbon nanoparticles and aggregates describedherein are characterized by Raman spectroscopy that is indicative of thehigh degree of order and uniformity of structure. In some embodiments,the uniform, ordered and/or pure carbon nanoparticles and aggregatesdescribed herein are produced using relatively high speed, low costimproved thermal reactors and methods, as described below. Additionaladvantages and/or improvements will also become apparent from thefollowing disclosure.

In the present disclosure, the term “graphene” refers to an allotrope ofcarbon in the form of a two-dimensional, atomic-scale, hexagonal latticein which one atom forms each vertex. The carbon atoms in graphene aresp²-bonded. Additionally, graphene has a Raman spectrum with two mainpeaks: a G-mode at approximately 1580 cm⁻¹ and a D-mode at approximately1350 cm⁻¹ (when using a 532 nm excitation laser).

In the present disclosure, the term “fullerene” refers to a molecule ofcarbon in the form of a hollow sphere, ellipsoid, tube, or other shapes.Spherical fullerenes can also be referred to as Buckminsterfullerenes,or buckyballs. Cylindrical fullerenes can also be referred to as carbonnanotubes. Fullerenes are similar in structure to graphite, which iscomposed of stacked graphene sheets of linked hexagonal rings.Fullerenes may also contain pentagonal (or sometimes heptagonal) rings.

In the present disclosure, the term “multi-walled fullerene” refers tofullerenes with multiple concentric layers. For example, multi-wallednanotubes (MWNTs) contain multiple rolled layers (concentric tubes) ofgraphene. Multi-walled spherical fullerenes (MWSFs) contain multipleconcentric spheres of fullerenes.

In the present disclosure, the term “nanoparticle” refers to a particlethat measures from 1 nm to 989 nm. The nanoparticle can include one ormore structural characteristics (e.g., crystal structure, defectconcentration, etc.), and one or more types of atoms. The nanoparticlecan be any shape, including but not limited to spherical shapes,spheroidal shapes, dumbbell shapes, cylindrical shapes, elongatedcylindrical type shapes, rectangular prism shapes, disk shapes, wireshapes, irregular shapes, dense shapes (i.e., with few voids), porousshapes (i.e., with many voids), etc.

In the present disclosure, the term “aggregate” refers to a plurality ofnanoparticles that are connected together by Van der Waals forces, bycovalent bonds, by ionic bonds, by metallic bonds, or by other physicalor chemical interactions. Aggregates can vary in size considerably, butin general are larger than about 500 nm.

In some embodiments, a carbon nanoparticle, as described herein,includes two or more connected multi-walled spherical fullerenes (MWSFs)and layers of graphene coating the connected MWSFs. In some embodiments,a carbon nanoparticle, as described herein, includes two or moreconnected multi-walled spherical fullerenes (MWSFs) and layers ofgraphene coating the connected MWSFs where the MWSFs do not contain acore composed of impurity elements other than carbon. In someembodiments, a carbon nanoparticle, as described herein, includes two ormore connected multi-walled spherical fullerenes (MWSFs) and layers ofgraphene coating the connected MWSFs where the MWSFs do not contain avoid (i.e., a space with no carbon atoms greater than approximately 0.5nm, or greater than approximately 1 nm) at the center. In someembodiments, the connected MWSFs are formed of concentric, well-orderedspheres of sp²-hybridized carbon atoms, as contrasted with spheres ofpoorly-ordered, non-uniform, amorphous carbon particles.

In some embodiments, the nanoparticles containing the connected MWSFshave an average diameter in a range from 5 to 500 nm, or from 5 to 250nm, or from 5 to 100 nm, or from 5 to 50 nm, or from 10 to 500 nm, orfrom 10 to 250 nm, or from 10 to 100 nm, or from 10 to 50 nm, or from 40to 500 nm, or from 40 to 250 nm, or from 40 to 100 nm, or from 50 to 500nm, or from 50 to 250 nm, or from 50 to 100 nm.

In some embodiments, the carbon nanoparticles described herein formaggregates, wherein many nanoparticles aggregate together to form alarger unit. In some embodiments, a carbon aggregate includes aplurality of carbon nanoparticles. A diameter across the carbonaggregate is in a range from 10 to 500 μm, or from 50 to 500 μm, or from100 to 500 μm, or from 250 to 500 μm, or from 10 to 250 μm, or from 10to 100 μm, or from 10 to 50 μm. In some embodiments, the aggregate isformed from a plurality of carbon nanoparticles, as defined above. Insome embodiments, aggregates contain connected MWSFs. In someembodiments, the aggregates contain connected MWSFs with a highuniformity metric (e.g., a ratio of graphene to MWSF from 20% to 80%), ahigh degree of order (e.g., a Raman signature with an ID/IG ratio from0.95 to 1.05), and a high degree of purity (e.g., greater than 99.9%carbon).

One benefit of producing aggregates of carbon nanoparticles,particularly with diameters in the ranges described above, is thataggregates of particles greater than 10 μm are easier to collect thanparticles or aggregates of particles that are smaller than 500 nm. Theease of collection reduces the cost of manufacturing equipment used inthe production of the carbon nanoparticles and increases the yield ofthe carbon nanoparticles. Additionally, particles greater than 10 μm insize pose fewer safety concerns compared to the risks of handlingsmaller nanoparticles, e.g., potential health and safety risks due toinhalation of the smaller nanoparticles. The lower health and safetyrisks, thus, further reduce the manufacturing cost.

In some embodiments, a carbon nanoparticle has a ratio of graphene toMWSFs from 10% to 90%, or from 10% to 80%, or from 10% to 60%, or from10% to 40%, or from 10% to 20%, or from 20% to 40%, or from 20% to 90%,or from 40% to 90%, or from 60% to 90%, or from 80% to 90%. In someembodiments, a carbon aggregate has a ratio of graphene to MWSFs is from10% to 90%, or from 10% to 80%, or from 10% to 60%, or from 10% to 40%,or from 10% to 20%, or from 20% to 40%, or from 20% to 90%, or from 40%to 90%, or from 60% to 90%, or from 80% to 90%. In some embodiments, acarbon nanoparticle has a ratio of graphene to connected MWSFs from 10%to 90%, or from 10% to 80%, or from 10% to 60%, or from 10% to 40%, orfrom 10% to 20%, or from 20% to 40%, or from 20% to 90%, or from 40% to90%, or from 60% to 90%, or from 80% to 90%. In some embodiments, acarbon aggregate has a ratio of graphene to connected MWSFs is from 10%to 90%, or from 10% to 80%, or from 10% to 60%, or from 10% to 40%, orfrom 10% to 20%, or from 20% to 40%, or from 20% to 90%, or from 40% to90%, or from 60% to 90%, or from 80% to 90%.

In some embodiments, Raman spectroscopy is used to characterize carbonallotropes to distinguish their molecular structures. For example,graphene can be characterized using Raman spectroscopy to determineinformation such as order/disorder, edge and grain boundaries,thickness, number of layers, doping, strain, and thermal conductivity.MWSFs have also been characterized using Raman spectroscopy to determinethe degree of order of the MWSFs.

In some embodiments, Raman spectroscopy is used to characterize thestructure of MWSFs or connected MWSFs. The main peaks in the Ramanspectra are the G-mode and the D-mode. The G-mode is attributed to thevibration of carbon atoms in sp²-hybridized carbon networks, and theD-mode is related to the breathing of hexagonal carbon rings withdefects. In some cases, defects may be present, yet may not bedetectable in the Raman spectra. For example, if the presentedcrystalline structure is orthogonal with respect to the basal plane, theD-peak will show an increase. On the other hand, if presented with aperfectly planar surface that is parallel with respect to the basalplane, the D-peak will be zero.

When using 532 nm incident light, the Raman G-mode is typically at 1582cm⁻¹ for planar graphite can be downshifted for MWSFs or connected MWSFs(e.g., down to 1565 cm⁻¹ or down to 1580 cm⁻¹). The D-mode is observedat approximately 1350 cm⁻¹ in the Raman spectra of MWSFs or connectedMWSFs. The ratio of the intensities of the D-mode peak to G-mode peak(i.e., the ID/IG) is related to the degree of order of the MWSFs, wherea lower ID/IG indicates a higher degree of order. An ID/IG near or below1 indicates a relatively high degree of order, and an ID/IG greater than1.1 indicates a lower degree of order.

In some embodiments, a carbon nanoparticle or a carbon aggregatecontaining MWSFs or connected MWSFs may have a Raman spectrum with afirst Raman peak at about 1350 cm⁻¹ and a second Raman peak at about1580 cm⁻¹ when using 532 nm incident light. In some embodiments, theratio of an intensity of the first Raman peak to an intensity of thesecond Raman peak (i.e., the ID/IG) for the nanoparticles or theaggregates described herein is in a range from 0.95 to 1.05, or from 0.9to 1.1, or from 0.8 to 1.2, or from 0.9 to 1.2, or from 0.8 to 1.1, orfrom 0.5 to 1.5, or less than 1.5, or less than 1.2, or less than 1.1,or less than 1, or less than 0.95, or less than 0.9, or less than 0.8.

In some embodiments, a carbon aggregate containing MWSFs or connectedMWSFs, as defined above, has a high purity. In some embodiments, thecarbon aggregate containing MWSFs or connected MWSFs has a ratio ofcarbon to metals of greater than 99.99%, or greater than 99.95%, orgreater than 99.9%, or greater than 99.8%, or greater than 99.5%, orgreater than 99%. In some embodiments, the carbon aggregate has a ratioof carbon to other elements of greater than 99.99%, or greater than99.95%, or greater than 99.9%, or greater than 99.5%, or greater than99%, or greater than 90%, or greater than 80%, or greater than 70%, orgreater than 60%. In some embodiments, the carbon aggregate has a ratioof carbon to other elements (except for hydrogen) of greater than99.99%, or greater than 99.95%, or greater than 99.9%, or greater than99.8%, or greater than 99.5%, or greater than 99%, or greater than 90%,or greater than 80%, or greater than 70%, or greater than 60%.

In some embodiments, a carbon aggregate containing MWSFs or connectedMWSFs, as defined above, has a high specific surface area. In someembodiments, the carbon aggregate has a Brunauer, Emmett and Teller(BET) specific surface area from 10 to 200 m²/g, or from 10 to 100 m²/g,or from 10 to 50 m²/g, or from 50 to 200 m²/g, or from 50 to 100 m²/g,or from 10 to 1000 m²/g.

In some embodiments, a carbon aggregate containing MWSFs or connectedMWSFs, as defined above, has a high electrical conductivity. In someembodiments, a carbon aggregate containing MWSFs or connected MWSFs, asdefined above, is compressed into a pellet and the pellet has anelectrical conductivity greater than 500 S/m, or greater than 1000 S/m,or greater than 2000 S/m, or greater than 3000 S/m, or greater than 4000S/m, or greater than 5000 S/m, or greater than 10000 S/m, or greaterthan 20000 S/m, or greater than 30000 S/m, or greater than 40000 S/m, orgreater than 50000 S/m, or greater than 60000 S/m, or greater than 70000S/m, or from 500 S/m to 100000 S/m, or from 500 S/m to 1000 S/m, or from500 S/m to 10000 S/m, or from 500 S/m to 20000 S/m, or from 500 S/m to100000 S/m, or from 1000 S/m to 10000 S/m, or from 1000 S/m to 20000S/m, or from 10000 to 100000 S/m, or from 10000 S/m to 80000 S/m, orfrom 500 S/m to 10000 S/m. In some cases, the density of the pellet isapproximately 1 g/cm³, or approximately 1.2 g/cm³, or approximately 1.5g/cm³, or approximately 2 g/cm³, or approximately 2.2 g/cm³, orapproximately 2.5 g/cm³, or approximately 3 g/cm³. Additionally, testshave been performed in which compressed pellets of the carbon aggregatematerials have been formed with compressions of 2000 psi and 12000 psiand with annealing temperatures of 800° C. and 1000° C. The highercompression and/or the higher annealing temperatures generally result inpellets with a higher degree of electrical conductivity, including inthe range of 12410.0 S/m to 13173.3 S/m.

High Purity Carbon Allotropes Produced Using Thermal Systems

In some embodiments, the carbon nanoparticles and aggregates describedherein are produced using thermal reactors and methods, such as anyappropriate thermal reactor and/or method. Further details pertaining tothermal reactors and/or methods of use can be found in U.S. Pat. No.9,862,602, issued Jan. 9, 2018, titled “CRACKING OF A PROCESS GAS”,which is hereby incorporated by reference in its entirety Additionally,precursors (e.g., including methane, ethane, propane, butane, andnatural gas) can be used with the thermal reactors to produce the carbonnanoparticles and the carbon aggregates described herein.

In some embodiments, the carbon nanoparticles and aggregates describedherein are produced using the thermal reactors with gas flow rates from1 standard liter per minute (slm) to 10 slm, or from 0.1 slm to 20 slm,or from 1 slm to 5 slm, or from 5 slm to 10 slm, or greater than 1 slm,or greater than 5 slm. In some embodiments, the carbon nanoparticles andaggregates described herein are produced using the thermal reactors withgas resonance times from 0.1 seconds to 30 seconds, or from 0.1 secondsto 10 seconds, or from 1 seconds to 10 seconds, or from 1 seconds to 5seconds, from 5 seconds to 10 seconds, or greater than 0.1 seconds, orgreater than 1 seconds, or greater than 5 seconds, or less than 30seconds.

In some embodiments, the carbon nanoparticles and aggregates describedherein are produced using the thermal reactors with production ratesfrom 10 g/hr to 200 g/hr, or from 30 g/hr to 200 g/hr, or from 30 g/hrto 100 g/hr, or from 30 g/hr to 60 g/hr, or from 10 g/hr to 100 g/hr, orgreater than 10 g/hr, or greater than 30 g/hr, or greater than 100 g/hr.

In some embodiments, thermal reactors or other cracking apparatuses andthermal reactor methods or other cracking methods can be used forrefining, pyrolyzing, dissociating or cracking feedstock process gasesinto its constituents to produce the carbon nanoparticles and the carbonaggregates described herein, as well as other solid and/or gaseousproducts (e.g., hydrogen gas and/or lower order hydrocarbon gases). Thefeedstock process gases generally include, for example, hydrogen gas(H²), carbon dioxide (CO²), C¹ to C¹⁰ hydrocarbons, aromatichydrocarbons, and/or other hydrocarbon gases such as natural gas,methane, ethane, propane, butane, isobutane, saturated/unsaturatedhydrocarbon gases, ethene, propene, etc., and mixtures thereof. Thecarbon nanoparticles and the carbon aggregates can include, for example,multi-walled spherical fullerenes (MWSFs), connected MWSFs, carbonnanospheres, graphene, graphite, highly ordered pyrolytic graphite,single-walled nanotubes, multi-walled nanotubes, other solid carbonproducts, and/or the carbon nanoparticles and the carbon aggregatesdescribed herein.

Some embodiments for producing the carbon nanoparticles and the carbonaggregates described herein include thermal cracking methods that use,for example, an elongated longitudinal heating element optionallyenclosed within an elongated casing, housing or body of a thermalcracking apparatus. The body generally includes, for example, one ormore tubes or other appropriate enclosures made of stainless steel,titanium, graphite, quartz, or the like. In some embodiments, the bodyof the thermal cracking apparatus is generally cylindrical in shape witha central elongate longitudinal axis arranged vertically and a feedstockprocess gas inlet at or near the top of the body. The feedstock processgas flows longitudinally down through the body or a portion thereof. Inthe vertical configuration, both gas flow and gravity assist in theremoval of the solid products from the body of the thermal crackingapparatus.

The heating element generally includes, for example, a heating lamp, oneor more resistive wires or filaments (or twisted wires), metalfilaments, metallic strips or rods, and/or other appropriate thermalradical generators or elements that can be heated to a specifictemperature (i.e., a molecular cracking temperature) sufficient tothermally crack molecules of the feedstock process gas. The heatingelement is generally disposed, located or arranged to extend centrallywithin the body of the thermal cracking apparatus along the centrallongitudinal axis thereof. For example, if there is only one heatingelement, then it is placed at or concentric with the centrallongitudinal axis, and if there is a plurality of the heating elements,then they are spaced or offset generally symmetrically or concentricallyat locations near and around and parallel to the central longitudinalaxis.

Thermal cracking to produce the carbon nanoparticles and aggregatesdescribed herein is generally achieved by passing the feedstock processgas over, or in contact with, or within the vicinity of, the heatingelement within a longitudinal elongated reaction zone generated by heatfrom the heating element and defined by and contained inside the body ofthe thermal cracking apparatus to heat the feedstock process gas to orat a specific molecular cracking temperature.

The reaction zone is considered to be the region surrounding the heatingelement and close enough to the heating element for the feedstockprocess gas to receive sufficient heat to thermally crack the moleculesthereof. The reaction zone is thus generally axially aligned orconcentric with the central longitudinal axis of the body. In someembodiments, the thermal cracking is performed under a specificpressure. In some embodiments, the feedstock process gas is circulatedaround or across the outside surface of a container of the reaction zoneor a heating chamber in order to cool the container or chamber andpreheat the feedstock process gas before flowing the feedstock processgas into the reaction zone.

In some embodiments, the carbon nanoparticles and aggregates describedherein and/or hydrogen gas are produced without the use of catalysts. Inother words, the process is catalyst free.

Some embodiments to produce the carbon nanoparticles and aggregatesdescribed herein using thermal cracking apparatuses and methods toprovide a standalone system that can advantageously be rapidly scaled upor scaled down for different production levels as desired. For example,some embodiments are scalable to provide a standalone hydrogen and/orcarbon nanoparticle producing station, a hydrocarbon source, or a fuelcell station. Some embodiments can be scaled up to provide highercapacity systems, e.g., for a refinery or the like.

In some embodiments, a thermal cracking apparatus for cracking afeedstock process gas to produce the carbon nanoparticles and aggregatesdescribed herein include a body, a feedstock process gas inlet, and anelongated heating element. The body has an inner volume with alongitudinal axis. The inner volume has a reaction zone concentric withthe longitudinal axis. A feedstock process gas is flowed into the innervolume through the feedstock process gas inlet during thermal crackingoperations. The elongated heating element is disposed within the innervolume along the longitudinal axis and is surrounded by the reactionzone. During the thermal cracking operations, the elongated heatingelement is heated by electrical power to a molecular crackingtemperature to generate the reaction zone, the feedstock process gas isheated by heat from the elongated heating element, and the heatthermally cracks molecules of the feedstock process gas that are withinthe reaction zone into constituents of the molecules.

In some embodiments, a method for cracking a feedstock process gas toproduce the carbon nanoparticles and aggregates described hereinincludes (1) providing a thermal cracking apparatus having an innervolume that has a longitudinal axis and an elongated heating elementdisposed within the inner volume along the longitudinal axis; (2)heating the elongated heating element by electrical power to a molecularcracking temperature to generate a longitudinal elongated reaction zonewithin the inner volume; (3) flowing a feedstock process gas into theinner volume and through the longitudinal elongated reaction zone (e.g.,wherein the feedstock process gas is heated by heat from the elongatedheating element); and (4) thermally cracking molecules of the feedstockprocess gas within the longitudinal elongated reaction zone intoconstituents thereof (e.g., hydrogen gas and one or more solid products)as the feedstock process gas flows through the longitudinal elongatedreaction zone.

In some embodiments, the feedstock process gas to produce the carbonnanoparticles and aggregates described herein includes a hydrocarbongas. The results of cracking include hydrogen (e.g., H²) and variousforms of the carbon nanoparticles and aggregates described herein. Insome embodiments, the carbon nanoparticles and aggregates include two ormore MWSFs and layers of graphene coating the MWSFs, and/or connectedMWSFs and layers of graphene coating the connected MWSFs. In someembodiments, the feedstock process gas is preheated (e.g., to 100° C. to500° C.) by flowing the feedstock process gas through a gas preheatingregion between a heating chamber and a shell of the thermal crackingapparatus before flowing the feedstock process gas into the innervolume. In some embodiments, a gas having nanoparticles therein isflowed into the inner volume and through the longitudinal elongatedreaction zone to mix with the feedstock process gas, and a coating of asolid product (e.g., layers of graphene) is formed around thenanoparticles.

Post-Processing High Purity Structured Carbons

In some embodiments, the carbon nanoparticles and aggregates containingmulti-walled spherical fullerenes (MWSFs) or connected MWSFs describedherein are produced and collected, and no post-processing is done. Inother embodiments, the carbon nanoparticles and aggregates containingmulti-walled spherical fullerenes (MWSFs) or connected MWSFs describedherein are produced and collected, and some post-processing is done.Some examples of post-processing involved in electromagnetic statesensing devices include mechanical processing such as ball milling,grinding, attrition milling, micro fluidizing, and other techniques toreduce the particle size without damaging the MWSFs.

Some further examples of post-processing include exfoliation processessuch as sheer mixing, chemical etching, oxidizing (e.g., Hummer method),thermal annealing, doping by adding elements during annealing (e.g.,sulfur, nitrogen), steaming, filtering, and lyophilizing, among others.Some examples of post-processing include sintering processes such asspark plasma sintering (SPS), direct current sintering, microwavesintering, and ultraviolet (UV) sintering, which can be conducted athigh pressure and temperature in an inert gas. In some embodiments,multiple post-processing methods can be used together or in a series. Insome embodiments, the post-processing produces functionalized carbonnanoparticles or aggregates containing multi-walled spherical fullerenes(MWSFs) or connected MWSFs.

In some embodiments, the materials are mixed together in differentcombinations. In some embodiments, different carbon nanoparticles andaggregates containing MWSFs or connected MWSFs described herein aremixed together before post-processing. For example, different carbonnanoparticles and aggregates containing MWSFs or connected MWSFs withdifferent properties (e.g., different sizes, different compositions,different purities, from different processing runs, etc.) can be mixedtogether. In some embodiments, the carbon nanoparticles and aggregatescontaining MWSFs or connected MWSFs described herein can be mixed withgraphene to change the ratio of the connected MWSFs to graphene in themixture. In some embodiments, different carbon nanoparticles andaggregates containing MWSFs or connected MWSFs described herein can bemixed together after post-processing. For example, different carbonnanoparticles and aggregates containing MWSFs or connected MWSFs withdifferent properties and/or different post-processing methods (e.g.,different sizes, different compositions, different functionality,different surface properties, different surface areas) can be mixedtogether.

In some embodiments, the carbon nanoparticles and aggregates describedherein are produced and collected, and subsequently processed bymechanical grinding, milling, and/or exfoliating. In some embodiments,the processing (e.g., by mechanical grinding, milling, exfoliating,etc.) reduces the average size of the particles. In some embodiments,the processing (e.g., by mechanical grinding, milling, exfoliating,etc.) increases the average surface area of the particles. In someembodiments, the processing by mechanical grinding, milling and/orexfoliation shears off some fraction of the carbon layers, producingsheets of graphite mixed with the carbon nanoparticles.

In some embodiments, the mechanical grinding or milling is performedusing a ball mill, a planetary mill, a rod mill, a shear mixer, ahigh-shear granulator, an autogenous mill, or other types of machiningused to break solid materials into smaller pieces by grinding, crushingor cutting. In some embodiments, the mechanical grinding, milling and/orexfoliating is performed wet or dry. In some embodiments, the mechanicalgrinding is performed by grinding for some period of time, then idlingfor some period of time, and repeating the grinding and idling for anumber of cycles. In some embodiments, the grinding period is from 1minute to 20 minutes, or from 1 minute to 10 minutes, or from 3 minutesto 8 minutes, or approximately 3 minutes, or approximately 8 minutes. Insome embodiments, the idling period is from 1 minute to 10 minutes, orapproximately 5 minutes, or approximately 6 minutes. In someembodiments, the number of grinding and idling cycles is from 1 minuteto 100 minutes, or from 5 minutes to 100 minutes, or from 10 minutes to100 minutes, or from 5 minutes to 10 minutes, or from 5 minutes to 20minutes. In some embodiments, the total amount of time of grinding andidling is from 10 minutes to 1200 minutes, or from 10 minutes to 600minutes, or from 10 minutes to 240 minutes, or from 10 minutes to 120minutes, or from 100 minutes to 90 minutes, or from 10 minutes to 60minutes, or approximately 90 minutes, or approximately 120 minutes.

In some embodiments, the grinding steps in the cycle are performed byrotating a mill in one direction for a first cycle (e.g., clockwise),and then rotating a mill in the opposite direction (e.g.,counterclockwise) for the next cycle. In some embodiments, themechanical grinding or milling is performed using a ball mill, and thegrinding steps are performed using a rotation speed from 100 to 1000rpm, or from 100 to 500 rpm, or approximately 400 rpm. In someembodiments, the mechanical grinding or milling is performed using aball mill that uses a milling media with a diameter from 0.1 mm to 20mm, or from 0.1 mm to 10 mm, or from 1 mm to 10 mm, or approximately 0.1mm, or approximately 1 mm, or approximately 10 mm. In some embodiments,the mechanical grinding or milling is performed using a ball mill thatuses a milling media composed of metal such as steel, an oxide such aszirconium oxide (zirconia), yttria stabilized zirconium oxide, silica,alumina, magnesium oxide, or other hard materials such as siliconcarbide or tungsten carbide.

In some embodiments, the carbon nanoparticles and aggregates describedherein are produced and collected, and subsequently processed usingelevated temperatures such as thermal annealing or sintering. In someembodiments, the processing using elevated temperatures is done in aninert environment such as nitrogen or argon. In some embodiments, theprocessing using elevated temperatures is done at atmospheric pressure,or under vacuum, or at low pressure. In some embodiments, the processingusing elevated temperatures is done at a temperature from 500° C. to2500° C., or from 500° C. to 1500° C., or from 800° C. to 1500° C., orfrom 800° C. to 1200° C., or from 800° C. to 1000° C., or from 2000° C.to 2400° C., or approximately 800° C., or approximately 1000° C., orapproximately 1500° C., or approximately 2000° C., or approximately2400° C.

In some embodiments, the carbon nanoparticles and aggregates describedherein are produced and collected, and subsequently, in post processingsteps, additional elements or compounds are added to the carbonnanoparticles, thereby incorporating the unique properties of the carbonnanoparticles and aggregates into other mixtures of materials.

In some embodiments, either before or after post-processing, the carbonnanoparticles and aggregates described herein are added to solids,liquids or slurries of other elements or compounds to form additionalmixtures of materials incorporating the unique properties of the carbonnanoparticles and aggregates. In some embodiments, the carbonnanoparticles and aggregates described herein are mixed with other solidparticles, polymers or other materials.

In some embodiments, either before or after post-processing, the carbonnanoparticles and aggregates described herein are used in variousapplications beyond applications pertaining to electromagnetic statesensing devices. Such applications including but not limited totransportation applications (e.g., automobile and truck tires,couplings, mounts, elastomeric O-rings, hoses, sealants, grommets, etc.)and industrial applications (e.g., rubber additives, functionalizedadditives for polymeric materials, additives for epoxies, etc.).

FIGS. 10A and 10B show transmission electron microscope (TEM) images ofas-synthesized carbon nanoparticles. The carbon nanoparticles of FIG.10A (at a first magnification) and FIG. 10B (at a second magnification)contain connected multi-walled spherical fullerenes 1002 (MWSFs) withgraphene layers 1004 that coat the connected MWSFs. The ratio of MWSF tographene allotropes in this example is approximately 80% due to therelatively short resonance times. The MWSFs in FIG. 10A areapproximately 5 nm to 10 nm in diameter, and the diameter can be from 5nm to 500 nm using the conditions described above. In some embodiments,the average diameter across the MWSFs is in a range from 5 nm to 500 nm,or from 5 nm to 250 nm, or from 5 nm to 100 nm, or from 5 nm to 50 nm,or from 10 nm to 500 nm, or from 10 nm to 250 nm, or from 10 nm to 100nm, or from 10 nm to 50 nm, or from 40 nm to 500 nm, or from 40 nm to250 nm, or from 40 nm to 100 nm, or from 50 nm to 500 nm, or from 50 nmto 250 nm, or from 50 nm to 100 nm. No catalyst was used in thisprocess, and therefore, there is no central seed containingcontaminants. The aggregate particles produced in this example had aparticle size of approximately 10 μm to 100 μm, or approximately 10 μmto 500 μm.

FIG. 10C shows the Raman spectrum of the as-synthesized aggregates inthis example taken with 532 nm incident light. The ID/IG for theaggregates produced in this example is from approximately 0.99 to 1.03,indicating that the aggregates were composed of carbon allotropes with ahigh degree of order.

FIG. 10D and FIG. 10E show example TEM images of the carbonnanoparticles after size reduction by grinding in a ball mill. The ballmilling was performed in cycles with a 3 minute counter-clockwisegrinding step, followed by a 6 minute idle step, followed by a 3 minuteclockwise grinding step, followed by a 6 minute idle step. The grindingsteps were performed using a rotation speed of 400 rpm. The millingmedia was zirconia and ranged in size from 0.1 mm to 10 mm. The totalsize reduction processing time was from 60 minutes to 120 minutes. Aftersize reduction, the aggregate particles produced in this example had aparticle size of approximately 1 μm to 5 μm. The carbon nanoparticlesafter size reduction are connected MWSFs with layers of graphene coatingthe connected MWSFs.

FIG. 10F shows a Raman spectrum from these aggregates after sizereduction taken with a 532 nm incident light. The ID/IG for theaggregate particles in this example after size reduction isapproximately 1.04. Additionally, the particles after size reduction hada Brunauer, Emmett and Teller (BET) specific surface area ofapproximately 40 m²/g to 50 m²/g.

The purity of the aggregates produced in this sample were measured usingmass spectrometry and x-ray fluorescence (XRF) spectroscopy. The ratioof carbon to other elements, except for hydrogen, measured in 16different batches was from 99.86% to 99.98%, with an average of 99.94%carbon.

In this example, carbon nanoparticles were generated using a thermalhot-wire processing system. The precursor material was methane, whichwas flowed from 1 slm to 5 slm. With these flow rates and the toolgeometry, the resonance time of the gas in the reaction chamber was fromapproximately 20 second to 30 seconds, and the carbon particleproduction rate was from approximately 20 g/hr.

Further details pertaining to such a processing system can be found inthe previously mentioned U.S. Pat. No. 9,862,602, titled “CRACKING OF APROCESS GAS.”

FIG. 10G, FIG. 10H and FIG. 10I show TEM images of as-synthesized carbonnanoparticles of this example. The carbon nanoparticles containconnected multi-walled spherical fullerenes (MWSFs) with layers ofgraphene coating the connected MWSFs. The ratio of multi-walledfullerenes to graphene allotropes in this example is approximately 30%due to the relatively long resonance times allowing thicker, or more,layers of graphene to coat the MWSFs. No catalyst was used in thisprocess, and therefore, there is no central seed containingcontaminants. The as-synthesized aggregate particles produced in thisexample had particle sizes of approximately 10 μm to 500 μm.

FIG. 10J shows a Raman spectrum from the aggregates of this example. TheRaman signature of the as-synthesized particles in this example isindicative of the thicker graphene layers which coat the MWSFs in theas-synthesized material. Additionally, the as-synthesized particles hada Brunauer, Emmett and Teller (BET) specific surface area ofapproximately 90 m²/g to 100 m²/g.

FIG. 10K and FIG. 10L show TEM images of the carbon nanoparticles ofthis example. Specifically, the images depict the carbon nanoparticlesafter performance of size reduction by grinding in a ball mill. The sizereduction process conditions were the same as those described aspertains to the foregoing FIG. 10G through FIG. 10J. After sizereduction, the aggregate particles produced in this example had aparticle size of approximately 1 μm to 5 μm. The TEM images show thatthe connected MWSFs that were buried in the graphene coating can beobserved after size reduction. FIG. 10M shows a Raman spectrum from theaggregates of this example after size reduction taken with 532 nmincident light. The ID/IG for the aggregate particles in this exampleafter size reduction is approximately 1, indicating that the connectedMWSFs that were buried in the graphene coating as-synthesized had becomedetectable in Raman after size reduction, and were well ordered. Theparticles after size reduction had a Brunauer, Emmett and Teller (BET)specific surface area of approximately 90 m²/g to 100 m²/g.

FIG. 10N is a scanning electron microscope (SEM) image of carbonaggregates showing the graphite and graphene allotropes at a firstmagnification. FIG. 10O is a SEM image of carbon aggregates showing thegraphite and graphene allotropes at a second magnification. The layeredgraphene is clearly shown within the distortion (wrinkles) of thecarbon. The 3D structure of the carbon allotropes is also visible.

The particle size distribution of the carbon particles of FIG. 10N andFIG. 10O is shown in FIG. 10P. The mass basis cumulative particle sizedistribution 1006 corresponds to the left y-axis in the graph (Q³(x)[%]). The histogram of the mass particle size distribution 1008corresponds to the right axis in the graph (dQ³(x) [%]). The medianparticle size is approximately 33 μm. The 10th percentile particle sizeis approximately 9 μm, and the 90th percentile particle size isapproximately 103 μm. The mass density of the particles is approximately10 g/L.

The particle size distribution of the carbon particles captured from amultiple-stage reactor is shown in FIG. 10Q. The mass basis cumulativeparticle size distribution 1014 corresponds to the left y-axis in thegraph (Q³(x) [%]). The histogram of the mass particle size distribution1016 corresponds to the right axis in the graph (dQ³(x) [%]). The medianparticle size captured is approximately 11 μm. The 10th percentileparticle size is approximately 3.5 μm, and the 90th percentile particlesize is approximately 21 μm. The graph in FIG. 10Q also shows the numberbasis cumulative particle size distribution 1018 corresponding to theleft y-axis in the graph (Q° (x) [Vo]). The median particle size bynumber basis is from approximately 0.1 μm to approximately 0.2 μm. Themass density of the particles collected is approximately 22 g/L.

Returning to the discussion of FIG. 10P, the graph also shows a secondset of example results. Specifically, in this example, the particleswere size-reduced by mechanical grinding, and then the size-reducedparticles were processed using a cyclone separator. The mass basiscumulative particle size distribution 1010 of the size-reduced carbonparticles captured in this example corresponds to the left y-axis in thegraph (Q³(x) [Vo]). The histogram of the mass basis particle sizedistribution 1012 corresponds to the right axis in the graph (dQ³(x)[Vo]). The median particle size of the size-reduced carbon particlescaptured in this example is approximately 6 μm. The 10th percentileparticle size is from 1 μm to 2 μm, and the 90th percentile particlesize is from 10 μm to 20 μm.

Further details pertaining to making and using cyclone separators can befound in U.S. Pat. No. 10,308,512 entitled “MICROWAVE REACTOR SYSTEMWITH GAS-SOLIDS SEPARATION,” which is hereby incorporated by referencein its entirety.

High Purity Carbon Allotropes Produced Using Microwave

In some cases, carbon particles and aggregates containing graphite,graphene and amorphous carbon can be generated using a microwave plasmareactor system using a precursor material that contains methane, orcontains isopropyl alcohol (IPA), or contains ethanol, or contains acondensed hydrocarbon (e.g., hexane). In some other examples, thecarbon-containing precursors are optionally mixed with a supply gas(e.g., argon). The particles produced in this example containedgraphite, graphene, amorphous carbon and no seed particles. Theparticles in this example had a ratio of carbon to other elements (otherthan hydrogen) of approximately 99.5% or greater.

In one particular example, a hydrocarbon was the input material for themicrowave plasma reactor, and the separated outputs of the reactorcomprised hydrogen gas and carbon particles containing graphite,graphene and amorphous carbon. The carbon particles were separated fromthe hydrogen gas in a multi-stage gas-solid separation system. Thesolids loading of the separated outputs from the reactor was from 0.001g/L to 2.5 g/L.

FIG. 10R, FIG. 10S, and FIG. 10T are TEM images of as-synthesized carbonnanoparticles. The images show examples of graphite, graphene andamorphous carbon allotropes. The layers of graphene and other carbonmaterials can be clearly seen in the images.

The particle size distribution of the carbon particles captured is shownin FIG. 10U. The mass basis cumulative particle size distribution 1020corresponds to the left y-axis in the graph (Q³(x) [%]). The histogramof the mass particle size distribution 1022 corresponds to the rightaxis in the graph (dQ³(x) [Vo]). The median particle size captured inthe cyclone separator in this example was approximately 14 μm. The 10thpercentile particle size was approximately 5 μm, and the 90th percentileparticle size was approximately 28 μm. The graph in FIG. 10U also showsthe number basis cumulative particle size distribution 1024corresponding to the left y-axis in the graph (Q⁰(x) [%]). The medianparticle size by number basis in this example was from approximately 0.1μm to approximately 0.2 μm.

FIG. 10V, FIG. 10W, and FIG. 10X, and FIG. 10Y are images that showthree-dimensional carbon-containing structures that are grown onto otherthree-dimensional structures. FIG. 10V is a 100× magnification ofthree-dimensional carbon structures grown onto carbon fibers, whereasFIG. 10W is a 200× magnification of three-dimensional carbon structuresgrown onto carbon fibers. FIG. 10X is a 1601× magnification ofthree-dimensional carbon structures grown onto carbon fibers. Thethree-dimensional carbon growth over the fiber surface is shown. FIG.10Y is a 10000× magnification of three-dimensional carbon structuresgrown onto carbon fibers. The image depicts growth onto the basal planeas well as onto edge planes.

More specifically, FIG. 10V thru FIG. 10Y show example SEM images of 3Dcarbon materials grown onto fibers using plasma energy from a microwaveplasma reactor as well as thermal energy from a thermal reactor. FIG.10V shows an SEM image of intersecting fibers 1031 and 1032 with 3Dcarbon material 1030 grown on the surface of the fibers. FIG. 10W is ahigher magnification image (the scale bar is 300 μm compared to 500 mfor FIG. 10V) showing 3D carbon growth 1030 on the fiber 1032.

FIG. 10X is a further magnified view (scale bar is 40 μm) showing 3Dcarbon growth 1030 on fiber surface 1035, where the 3D nature of thecarbon growth 1030 can be clearly seen. FIG. 10Y shows a close-up view(scale bar is 500 nm) of the carbon alone, showing interconnectionbetween basal planes 1036 and edge planes 1034 of numerous sub-particlesof the 3D carbon material grown on the fiber. FIG. 10V through FIG. 10Ydemonstrate the ability to grow 3D carbon on a 3D fiber structureaccording to some embodiments, such as 3D carbon growth grown on a 3Dcarbon fiber.

In some embodiments, 3D carbon growth on fibers can be achieved byintroducing a plurality of fibers into the microwave plasma reactor andusing plasma in the microwave reactor to etch the fibers. The etchingcreates nucleation sites such that when carbon particles andsub-particles are created by hydrocarbon disassociation in the reactor,growth of 3D carbon structures is initiated at these nucleation sites.The direct growth of the 3D carbon structures on the fibers, whichthemselves are three-dimensional in nature, provides a highlyintegrated, 3D structure with pores into which resin can permeate. This3D reinforcement matrix (including the 3D carbon structures integratedwith high aspect ratio reinforcing fibers) for a resin composite resultsin enhanced material properties, such as tensile strength and shear,compared to composites with conventional fibers that have smoothsurfaces and which smooth surfaces typically delaminate from the resinmatrix.

In some embodiments, carbon materials, such as 3D carbon materialsdescribed herein, can be functionalized to promote adhesion and/or addelements such as oxygen, nitrogen, carbon, silicon, or hardening agents.In some embodiments, the carbon materials can be functionalized insitu—that is, within the same reactor in which the carbon materials areproduced. In some embodiments, the carbon materials can befunctionalized in post-processing. For example, the surfaces offullerenes or graphene can be functionalized with oxygen- ornitrogen-containing species which form bonds with polymers of the resinmatrix, thus improving adhesion and providing strong binding to enhancethe strength of composites.

Embodiments include functionalizing surface treatments for carbon (e.g.,CNTs, CNO, graphene, 3D carbon materials such as 3D graphene) utilizingplasma reactors (e.g., microwave plasma reactors) described herein.Various embodiments can include in situ surface treatment duringcreation of carbon materials that can be combined with a binder orpolymer in a composite material. Various embodiments can include surfacetreatment after creation of the carbon materials while the carbonmaterials are still within the reactor.

In the foregoing specification, the disclosure has been described withreference to specific embodiments thereof. It will however be evidentthat various modifications and changes may be made thereto withoutdeparting from the broader spirit and scope of the disclosure. Forexample, the above-described process flows are described with referenceto a particular ordering of process actions. However, the ordering ofmany of the described process actions may be changed without affectingthe scope or operation of the disclosure.

The specification and drawings are to be regarded in an illustrativesense rather than in a restrictive sense.

What is claimed is:
 1. A container, comprising: a surface defining avolume of the container; a first resonance portion disposed on a firstportion of the surface of the container using one or more firstcarbon-based inks, the first resonance portion configured to resonatewithin a first range of frequencies in response to one or moreelectromagnetic pings received from a user device; and a secondresonance portion disposed on a second portion of the surface of thecontainer using one or more second carbon-based inks different than theone or more first carbon-based inks, the second resonance portionconfigured to resonate within a second range of frequencies in responseto the one or more electromagnetic pings, the second range offrequencies being different than the first range of frequencies.
 2. Thecontainer of claim 1, wherein: the first resonance portion includes afirst assembly of three-dimensional (3D) carbon-containing structuresprinted on the first portion of the surface of the container; and thesecond resonance portion includes a second assembly of 3Dcarbon-containing structures printed on the second portion of thesurface of the container.
 3. The container of claim 1, wherein: aresonant frequency of the first resonance portion is based at least inpart on a surface area of the first portion of the surface of thecontainer; and a resonant frequency of the second resonance portion isbased at least in part on a surface area of the second portion of thesurface of the container.
 4. The container of claim 1, wherein: aresonant frequency of the first resonance portion is based at least inpart on a geometry of the first portion of the surface of the container;and a resonant frequency of the second resonance portion is based atleast in part on a geometry of the second portion of the surface of thecontainer.
 5. The container of claim 1, wherein the first portion of thesurface of the container has a different physical geometry than thesecond portion of the surface of the container.
 6. The container ofclaim 1, wherein a size of the first portion of the surface of thecontainer is different than a size of second portion of the surface ofthe container.
 7. The container of claim 1, wherein a resonant frequencyof at least one of the first resonance portion or the second resonanceportion is based at least in part on a permeability of the container. 8.The container of claim 1, wherein the first resonance portion isconfigured to indicate a presence of an item within the container byresonating within the first range of frequencies in response to the oneor more electromagnetic pings.
 9. The container of claim 8, wherein theitem comprises an analyte, and a resonant frequency of the firstresonance portion is based at least in part on one or morecharacteristics of the analyte.
 10. The container of claim 8, whereinthe second resonance portion is configured to indicate state informationof the item by resonating within the second range of frequencies inresponse to the one or more electromagnetic pings.
 11. The container ofclaim 10, wherein the state information includes one or more of aquantity of the item within the container, a potency of the item withinthe container, or a staleness of the item within the container.
 12. Thecontainer of claim 10, further comprising: a third resonance portiondisposed on a third portion of the surface of the container using one ormore third carbon-based inks different than the one or more firstcarbon-based inks and the one or more second carbon-based inks, thethird resonance portion configured to resonate within a third range offrequencies in response to the one or more electromagnetic pings. 13.The container of claim 12, wherein the third resonance portion isconfigured to indicate product identification information of the item byresonating within the third range of frequencies in response to the oneor more electromagnetic pings.
 14. The container of claim 13, whereinthe product identification information includes a product code or aproduct ID of the item.
 15. The container of claim 12, wherein: thefirst resonance portion includes a first assembly of three-dimensional(3D) carbon-containing structures printed on the first portion of thesurface of the container; the second resonance portion includes a secondassembly of 3D carbon-containing structures printed on the secondportion of the surface of the container; and the third resonance portionincludes a third assembly of 3D carbon-containing structures printed onthe third portion of the surface of the container, wherein each of thefirst, second, and third assemblies of 3D carbon-containing structuresis configured to resonate at a different frequency in response to theone or more electromagnetic pings.
 16. The container of claim 1, whereinthe first resonance portion is configured to: indicate a presence of ananalyte by resonating at a first frequency in response to the one ormore electromagnetic pings; and indicate an absence of the analyte byresonating at a second frequency in response to the one or moreelectromagnetic pings, the second frequency being different than thefirst frequency.
 17. The container of claim 16, wherein the firstresonance portion includes a material that is sensitive to the presenceof the analyte.
 18. The container of claim 17, wherein a capacitance ofthe material is based at least in part on the presence of the analytewithin the container.
 19. The container of claim 17, wherein thematerial comprises a redox mediator.
 20. The container of claim 1,wherein the user device is a smartphone, a radio frequencyidentification (RFID) reader, or a near-field communication (NFC)device.